CN110139842A - Intermediate film for laminated glasses and laminated glass - Google Patents

Intermediate film for laminated glasses and laminated glass Download PDF

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Publication number
CN110139842A
CN110139842A CN201880005981.5A CN201880005981A CN110139842A CN 110139842 A CN110139842 A CN 110139842A CN 201880005981 A CN201880005981 A CN 201880005981A CN 110139842 A CN110139842 A CN 110139842A
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CN
China
Prior art keywords
layer
mentioned
covering portion
intermediate film
laminated
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Granted
Application number
CN201880005981.5A
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Chinese (zh)
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CN110139842B (en
Inventor
岩本达矢
坂本悠
石川由贵
河田晋治
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Sekisui Chemical Co Ltd
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Sekisui Chemical Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
    • B32B17/10036—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising two outer glass sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10165—Functional features of the laminated safety glass or glazing
    • B32B17/10293—Edge features, e.g. inserts or holes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10605—Type of plasticiser
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    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
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    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10678—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer comprising UV absorbers or stabilizers, e.g. antioxidants
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    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10688—Adjustment of the adherence to the glass layers
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    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10743—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing acrylate (co)polymers or salts thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10761—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing vinyl acetal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
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    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/02—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by features of form at particular places, e.g. in edge regions
    • B32B3/04—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by features of form at particular places, e.g. in edge regions characterised by at least one layer folded at the edge, e.g. over another layer ; characterised by at least one layer enveloping or enclosing a material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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    • B32B2250/03—3 layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/10—Properties of the layers or laminate having particular acoustical properties
    • B32B2307/102—Insulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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    • B32B2333/00—Polymers of unsaturated acids or derivatives thereof
    • B32B2333/04—Polymers of esters
    • B32B2333/12—Polymers of methacrylic acid esters, e.g. PMMA, i.e. polymethylmethacrylate
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B2605/00—Vehicles
    • B32B2605/006—Transparent parts other than made from inorganic glass, e.g. polycarbonate glazings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2329/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Joining Of Glass To Other Materials (AREA)
  • Laminated Bodies (AREA)

Abstract

The present invention provides a kind of sound-proofing that laminated glass can be improved and the intermediate film for laminated glasses for making end be not likely to produce foaming.Intermediate film for laminated glasses of the invention has first layer and coats at least part of side covering portion of the side of the first layer, the first layer is 0.17MPa hereinafter, and modulus of shearing of the side covering portion at 25 DEG C is more than 1MPa in the modulus of shearing at 25 DEG C.

Description

Intermediate film for laminated glasses and laminated glass
Technical field
The present invention relates to the intermediate film for laminated glasses to obtain laminated glass.Moreover, it relates to using above-mentioned The laminated glass of intermediate film for laminated glasses.
Background technique
Even if laminated glass is generated breakage by external impact, glass fragment is also rare to disperse, and safety is excellent.Cause This, above-mentioned laminated glass has been widely used for automobile, rail vehicle, aircraft, ship and building etc..Above-mentioned laminated glass is logical It crosses and sandwiches intermediate film for laminated glasses between 2 glass sheets and manufacture.
As above-mentioned intermediate film for laminated glasses, the intermediate coat including the single layer with 1 layer of structure is tied with 2 layers or more The intermediate coat of the multilayer of structure.
As an example of above-mentioned intermediate film for laminated glasses, the following patent document 1 discloses a kind of puigging, packets Contain: acetalizing degree is in 100 parts by weight of polyvinyl acetal resin, alkali metal salt and the alkali salt of 60~85 moles of % Plasticizer more than at least one 0.001~1.0 parts by weight of metal salt and 30 parts by weight.The puigging can be with single layer quilt As intermediate coat.
In turn, it is also described in following patent documents 1 a kind of by above-mentioned puigging and multilayer made of other layer laminates Intermediate coat.Other layers being laminated on puigging include: acetalizing degree is the polyvinyl acetal resin 100 of 60~85 moles of % 0.001~1.0 parts by weight of at least one of parts by weight, alkali metal salt and alkali salt metal salt and 30 parts by weight with Under plasticizer.
A kind of intermediate coat is disclosed in following patent documents 2, it includes the first springforms with 1MPa~20MPa or so The first area of amount, the second area with the second elasticity modulus with 2~15MPa or so.Second area may enclose The periphery in one region.
It discloses and a kind of is provided between two resin layers (A) comprising clear adhesive resin in following patent documents 3 The intermediate coat of resin layer (B) comprising polyethylene terephthalate.The end of resin layer (A) is relative to resin layer (B) It is prominent for end.The end of resin layer (B) can also be covered by the end of resin layer (A).
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2007-070200 bulletin
Patent document 2:WO2015/054112A1
Patent document 3: Japanese Unexamined Patent Publication 2008-303084 bulletin
Summary of the invention
Problems to be solved by the invention
For the comfort of car steering, it is desirable that mitigate interior noise.It as interior noise, can enumerate: because engine drives And the noise of generation, when driving noise, the noise generated when driving by body oscillating as caused by the tread contour of tire, The noise generated when driving by suspension vibration and the noise etc. generated when driving by wind.For such noise, it is expected that mentioning Laminated glass is risen in the sound-proofing of the intermediate frequency zone of 2000Hz~4000Hz.
In addition, in recent years, from using the fuel automobile of internal combustion engine to electric car transition.It, can as electric car Enumerate: using electric motor electric car and the mixed power electric car etc. of internal combustion engine and electric motor is applied in combination. In electric car, can generate because of the driving of electric motor is being more than the noise of the high frequency region of 4000Hz.For electric car For, it is expected that promoting laminated glass is being more than the sound-proofing of the high frequency region of 4000Hz.It should be noted that for using internal combustion engine Fuel automobile, it is also desirable to laminated glass be more than the high frequency region of 4000Hz sound-proofing it is excellent.
It should be noted that for the laminated glass used in building etc., it is also desirable to from intermediate frequency zone to high frequency region Sound-proofing it is excellent.
However, for having used the laminated glass of the existing intermediate coat as recording in Patent Documents 1 to 3, sometimes Sound-proofing is unable to fully improve
In addition, as a result having obtained following opinion present inventor has performed research: passing through reduction intermediate coat cutting at room temperature Sound-proofing can be improved in shear modulu.In addition, the present inventor is it has been investigated that following projects: if in order to improve sound-proofing The modulus of shearing of intermediate coat at room temperature is reduced, then may cause and generate foaming or hair in the end of the intermediate coat of laminated glass The plate offset of raw laminated glass.
The purpose of the present invention is to provide a kind of sound-proofing that laminated glass can be improved and foaming is not likely to produce in end Intermediate film for laminated glasses.In addition, the object of the invention is also to provide the interlayers for having used above-mentioned intermediate film for laminated glasses Glass.
Solution to the problem
Extensive aspect according to the present invention, it is possible to provide a kind of intermediate film for laminated glasses is (hereinafter sometimes referred to as intermediate Film), for the intermediate film for laminated glasses with 1 layer of structure or 2 layers or more structure, wherein the intermediate coat have first layer and Side covering portion, the first layer have opposite the 1st interarea and the 2nd interarea and above-mentioned 1st interarea of connection and above-mentioned the The side of 2 interareas, the side covering portion coat at least part of the above-mentioned side of above-mentioned first layer, and above-mentioned first layer is 25 Modulus of shearing at DEG C is 0.17MPa hereinafter, and modulus of shearing of the above-mentioned side covering portion at 25 DEG C is more than 1MPa.
The particular aspects of intermediate coat according to the present invention, wherein above-mentioned first layer includes thermoplastic resin, or comprising making Solidfied material made of photocurable compound or moisture-curable compound cures.
The particular aspects of intermediate coat according to the present invention, wherein above-mentioned first layer includes thermoplastic resin and plasticizer.
The particular aspects of intermediate coat according to the present invention, wherein above-mentioned side covering portion includes thermoplastic resin and plasticising Agent.
The particular aspects of intermediate coat according to the present invention, wherein above-mentioned first layer includes thermoplastic resin and plasticizer, on Stating side covering portion includes thermoplastic resin and plasticizer, and above-mentioned plasticizer is relative in above-mentioned first layer in above-mentioned first layer The contents of 100 parts by weight of thermoplastic resin is stated than above-mentioned plasticizer in above-mentioned side covering portion relative in above-mentioned side covering portion It is more than more 15 parts by weight of the content of above-mentioned 100 parts by weight of thermoplastic resin.
The particular aspects of intermediate coat according to the present invention, wherein above-mentioned side covering portion with a thickness of 0.05mm or more and 2mm or less.
The particular aspects of intermediate coat according to the present invention, wherein at 1 week of the above-mentioned side as above-mentioned first layer periphery Distance 100% in, by above-mentioned side covering portion cladding side distance be 15% or more and 100% or less.
The particular aspects of intermediate coat according to the present invention, wherein the total surface area in the above-mentioned side of above-mentioned first layer In 100%, the surface area by above-mentioned side covering portion cladding is 15% or more and 100% or less.
The particular aspects of intermediate coat according to the present invention, wherein above-mentioned intermediate coat is the interlayer glass with 2 layers or more structures Glass intermediate coat has the second layer on above-mentioned 1st interarea for being set to above-mentioned first layer.
The particular aspects of intermediate coat according to the present invention, wherein the above-mentioned second layer extends to the above-mentioned side of above-mentioned first layer At least part in portion, thus coats at least part of the above-mentioned side of above-mentioned first layer, to be made of the above-mentioned second layer Above-mentioned side covering portion.
The particular aspects of intermediate coat according to the present invention, wherein the material of the above-mentioned second layer and above-mentioned side covering portion Material is different.
The particular aspects of intermediate coat according to the present invention, wherein the above-mentioned second layer includes thermoplastic resin and plasticizer.
The particular aspects of intermediate coat according to the present invention, wherein above-mentioned intermediate coat is the interlayer glass for having the above structure that haves three layers Glass intermediate coat has the third layer on above-mentioned 2nd interarea for being set to above-mentioned first layer.
The particular aspects of intermediate coat according to the present invention, wherein above-mentioned third layer extends to the above-mentioned side of above-mentioned first layer At least part in portion, thus coats at least part of the above-mentioned side of above-mentioned first layer, to be made of above-mentioned third layer Above-mentioned side covering portion.
The particular aspects of intermediate coat according to the present invention, wherein the material of above-mentioned third layer and above-mentioned side covering portion Material is different.
The particular aspects of intermediate coat according to the present invention, wherein above-mentioned third layer includes thermoplastic resin and plasticizer.
The particular aspects of intermediate coat according to the present invention, wherein when the thickness of intermediate coat is denoted as T, above-mentioned first layer With a thickness of 0.06T or more.
Extensive aspect according to the present invention, it is possible to provide a kind of laminated glass has: the 1st laminated glass member, the 2nd folder Layer glass component and above-mentioned intermediate film for laminated glasses, in above-mentioned 1st laminated glass member and above-mentioned 2nd laminated glass Above-mentioned intermediate film for laminated glasses is provided between component.
The particular aspects of laminated glass according to the present invention, wherein wrap the above-mentioned side of above-mentioned intermediate film for laminated glasses The portion of covering extends at least part of the side of above-mentioned 1st laminated glass member and above-mentioned 2nd laminated glass member.
The effect of invention
Intermediate film for laminated glasses of the invention has 1 layer of structure or 2 layers or more structure.In laminated glass-use of the invention Between film have a first layer and side covering portion, the first layer has opposite the 1st interarea and the 2nd interarea and connection above-mentioned The side of 1st interarea and above-mentioned 2nd interarea, the side covering portion are coated at least one of the above-mentioned side of above-mentioned first layer Point.In intermediate film for laminated glasses of the invention, modulus of shearing of the above-mentioned first layer at 25 DEG C is 0.17MPa hereinafter, simultaneously And modulus of shearing of the above-mentioned side covering portion at 25 DEG C is more than 1MPa.On having due to intermediate film for laminated glasses of the invention Composition is stated, therefore in the present invention, sound-proofing can be improved, and end is made to be not likely to produce foaming.
Detailed description of the invention
Fig. 1 (a) and (b) be schematically show the 1st embodiment of the invention intermediate film for laminated glasses it is vertical Body figure and cross-sectional view.
Fig. 2 is the perspective view for schematically showing the intermediate film for laminated glasses of the 2nd embodiment of the invention.
Fig. 3 is the perspective view for schematically showing the intermediate film for laminated glasses of the 3rd embodiment of the invention.
Fig. 4 is the perspective view for schematically showing the intermediate film for laminated glasses of the 4th embodiment of the invention.
Fig. 5 is the perspective view for schematically showing the intermediate film for laminated glasses of the 5th embodiment of the invention.
Fig. 6 is the perspective view for schematically showing the intermediate film for laminated glasses of the 6th embodiment of the invention.
Fig. 7 is the perspective view for schematically showing the intermediate film for laminated glasses of the 7th embodiment of the invention.
Fig. 8 is the perspective view for schematically showing the intermediate film for laminated glasses of the 8th embodiment of the invention.
Fig. 9 is the perspective view for schematically showing the intermediate film for laminated glasses of the 9th embodiment of the invention.
Figure 10 is the perspective view for schematically showing the intermediate film for laminated glasses of the 10th embodiment of the invention.
Figure 11 is the perspective view for schematically showing the intermediate film for laminated glasses of the 11st embodiment of the invention.
Figure 12 is the cross-sectional view for schematically showing the laminated glass of the 1st embodiment.
Figure 13 is the cross-sectional view for schematically showing the laminated glass of the 2nd embodiment.
Symbol description
1,1A, 1B, 1C, 1D, 1E, 1F, 1G, 1H, 1I, 1J, 1X ... first layer
2,2A, 2B, 2C, 2D, 2E, 2F, 2G ... second layer
3,3A, 3B, 3C, 3D, 3E ... third layer
4, the side 4A, 4B, 4C, 4D, 4E, 4F, 4G, 4H, 4I, 4J, 4X ... covering portion
11,11A, 11B, 11C, 11D, 11E, 11F, 11G, 11H, 11I, 11J, 11X ... intermediate coat
21, the first laminated glass member of 21X ...
22, the second laminated glass member of 22X ...
31,31X ... laminated glass
Specific embodiment
Hereinafter, explaining the present invention in detail.
There are intermediate film for laminated glasses (hereinafter sometimes referred to as intermediate coat) of the invention 1 layer of structure or 2 layers or more to tie Structure.Intermediate coat of the invention can have 1 layer of structure, can also have 2 layers or more structures.Intermediate coat of the invention can have the double-deck knot Structure can also have the above structure that haves three layers.Intermediate coat of the invention can be the intermediate coat with 1 layer of structure for only having first layer (intermediate coat of single layer) is also possible to the intermediate coat (centre of multilayer for having 2 layers or more structures of first layer and other layers Film).
Intermediate coat of the invention has first layer.First layer has opposite the 1st interarea and the 2nd interarea and connection The side of above-mentioned 1st interarea and above-mentioned 2nd interarea.
In intermediate coat of the invention, modulus of shearing of the above-mentioned first layer at 25 DEG C is 0.17MPa hereinafter, and above-mentioned side Modulus of shearing of portion's covering portion at 25 DEG C is more than 1MPa.
Since intermediate coat of the invention has above-mentioned composition, in the present invention, sound-proofing can be improved, and make end not It is also easy to produce foaming.
Since the modulus of shearing of above-mentioned first layer is smaller, sound-proofing is got higher.On the other hand, due to above-mentioned first layer At least part of side is sheared the biggish side covering portion cladding of modulus, therefore end can be made to be not likely to produce foaming.In turn, Since at least part of the side of above-mentioned first layer is sheared the biggish side covering portion cladding of modulus, interlayer can inhibit The plate of glass deviates.
It should be noted that so-called plate offset refers to: for example protecting laminated glass in hot environment with upright state Guan Shi, under the gravity of glass plate, the phenomenon that offset has occurred relative to the glass plate of the other side in the glass plate of side.
From the viewpoint of further increasing sound-proofing, modulus of shearing of the above-mentioned first layer at 25 DEG C is preferably 0.165MPa is hereinafter, more preferably 0.16MPa or less.Modulus of shearing of the above-mentioned first layer at 25 DEG C can for 0.01MPa with On.
From the viewpoint of further suppressing the foaming of end, further suppressing plate offset, above-mentioned side covering portion is 25 Modulus of shearing at DEG C is preferably 3MPa or more, more preferably 5MPa or more.Shearing mould of the above-mentioned side covering portion at 25 DEG C Amount can be 100MPa or less.
Hereinafter, being illustrated in conjunction with attached drawing to a specific embodiment of the invention.
Fig. 1 (a) and be (b) intermediate film for laminated glasses for schematically showing the 1st embodiment of the invention Perspective view and cross-sectional view.Fig. 1 (b) is the cross-sectional view of the X-X line along Fig. 1 (a).It should be noted that in Fig. 1 and aftermentioned In figure, different positions can be replaced mutually.
Intermediate coat 11 shown in FIG. 1 is the intermediate coat of the multilayer with 2 layers or more structures, specifically has the knot that haves three layers The intermediate coat of the multilayer of structure.Intermediate coat 11 can be used for obtaining laminated glass.Intermediate coat 11 is intermediate film for laminated glasses.Intermediate coat 11 flat shape is quadrangle.
Intermediate coat 11 has first layer 1, the second layer 2 and third layer 3.Intermediate coat 11 has side covering portion 4.
First layer 1 has opposite the 1st interarea and the 2nd interarea.First layer 1 has the 1st interarea of connection and the 2nd interarea Side.In the present embodiment, side is planar, as side.First layer 1 has 4 sides.It should be noted that side It is also possible to threadiness.The end of first layer is also possible to the shape that front end attenuates.
The second layer 2 is arranged and is stacked on the 1st interarea of first layer 1.Third layer 3 is arranged and is stacked on the 2nd of first layer 1 On interarea.First layer 1 is middle layer.The second layer 2 and third layer 3 are respectively protective layer, are in the present embodiment superficial layer. First layer 1 is arranged and is sandwiched between the second layer 2 and third layer 3.Therefore, intermediate coat 11 have the second layer 2, first layer 1 and The sequentially multilayered structure (2/ first layer of the second layer, 1/ third layer 3) made of lamination of third layer 3.
It should be noted that respectively can be between the second layer 2 and first layer 1 and between first layer 1 and third layer 3 Other layers are set.The second layer 2 and first layer 1 and first layer 1 and third layer 3 are respectively preferably direct lamination.
Side covering portion 4 is coated with the entire side of first layer 1.Specifically, 4 sides of first layer 1 are all by side Portion's covering portion 4 coats.
The second layer 2 extends to the center of the above-mentioned side of first layer 1.The second layer 2 is coated with the above-mentioned of first layer 1 as a result, The half region of side.Side covering portion 4 is constituted by the second layer 2.
Third layer 3 extends to the center of the above-mentioned side of first layer 1.Third layer 3 is coated with the above-mentioned of first layer 1 as a result, The half region of side.Side covering portion 4 is constituted by third layer 3.
Therefore, covering portion 4 entirety in side is made of the second layer 2 and third layer 3.
It is whole that first layer 1 is coated with by the second layer 2 and third layer 3.
It is also possible in the second layer and third layer that only the second layer extends to the side of first layer, can also be that only third layer is prolonged Extend to the side of first layer.
Fig. 2 is the perspective view for schematically showing the intermediate film for laminated glasses of the 2nd embodiment of the invention.
Intermediate coat 11A shown in Fig. 2 has first layer 1A, second layer 2A and third layer 3A.Intermediate coat 11A has side Portion covering portion 4A.Different from intermediate coat 11, in intermediate coat 11A, 2 side quilts only opposite in 4 sides of first layer 1A Side covering portion 4A coats (right side and left side of Fig. 2).Side covering portion 4A is constituted by second layer 2A and third layer 3A.First layer Opposite 2 side in 4 sides of 1A is not coated by side covering portion 4A but exposes (the nearby side and inboard of Fig. 2).
For the case where being constituted as intermediate coat 11A and following intermediate coat 11C, 11E, 11F, 11I, such as It, can be by make side covering portion 4A, 4C, 4E, 4F, 4I be located at the upper and lower mode of windshield in the windshield of automobile Setting, so that plate be further prevented to deviate.
In addition, in the windshield of automobile, sometimes to make only 2 mode covered when being easy by visuognosis and 2 Windshield is set.In this case, intermediate coat 11A, 11C, 11E, 11F, 11I are preferably used.
Fig. 3 is the perspective view for schematically showing the intermediate film for laminated glasses of the 3rd embodiment of the invention.
Intermediate coat 11B shown in Fig. 3 has first layer 1B, second layer 2B and third layer 3B.Intermediate coat 11B has side Portion covering portion 4B.Different from intermediate coat 11, in intermediate coat 11B, only 1 side is wrapped by side in 4 sides of first layer 1B Cover portion 4B cladding (left side of Fig. 3).Side covering portion 4B is constituted by second layer 2B and third layer 3B.4 sides of first layer 1B In 3 sides not by side covering portion 4B coat but expose (nearby side, inboard and the right side of Fig. 3).
For the case where being constituted as intermediate coat 11B and following intermediate coat 11D, 11G, 11J, such as in vapour In the windshield of vehicle, it can be arranged in a manner of making side covering portion 4B, 4D, 4G, 4J be located at the lower section of windshield, from And plate is further prevented to deviate.
In addition, in the windshield of automobile, sometimes so that only 1 when (such as top) is easy by visuognosis and 3 quilt Windshield is arranged in the mode of covering.In this case, intermediate coat 11B, 11D, 11G, 11J are preferably used.
Fig. 4 is the perspective view for schematically showing the intermediate film for laminated glasses of the 4th embodiment of the invention.
Intermediate coat 11C shown in Fig. 4 has first layer 1C, second layer 2C, third layer 3C and side covering portion 4C.No It is same as intermediate coat 11, in intermediate coat 11C, 2 sides only opposite are by side covering portion 4C packet in 4 sides of first layer 1C Cover (right side and left side of Fig. 4).The material of side covering portion 4C is different from the material of second layer 2C and third layer 3C.Side cladding Portion 4C is formed from second layer 2C and third layer 3C by different resin combinations.With being different from second layer 2C and third layer 3C, Additionally constitute side covering portion 4C.Opposite 2 side in 4 sides of first layer 1C is not by side covering portion 4C packet It covers but exposes (the nearby side and inboard of Fig. 4).The side of side covering portion 4C uncoated second layer 2C and third layer 3C.
Fig. 5 is the perspective view for schematically showing the intermediate film for laminated glasses of the 5th embodiment of the invention.
Intermediate coat 11D shown in fig. 5 has first layer 1D, second layer 2D, third layer 3D and side covering portion 4D.No Be same as intermediate coat 11, in intermediate coat 11D, in 4 sides of first layer 1D only 1 side by side covering portion 4D coat (Fig. 5 Left side).The material of side covering portion 4D is different from the material of second layer 2D and third layer 3D.Side covering portion 4D and the second layer 2D and third layer 3D are formed by different resin combinations.With being different from second layer 2D and third layer 3D, it additionally constitutes Side covering portion 4D.3 sides in 4 sides of first layer 1D are not coated by side covering portion 4D but expose (Fig. 5's Nearby side, inboard and right side).The side of side covering portion 4D uncoated second layer 2D and third layer 3D.
Fig. 6 is the perspective view for schematically showing the intermediate film for laminated glasses of the 6th embodiment of the invention.
Intermediate coat 11E shown in fig. 6 has first layer 1E, second layer 2E, third layer 3E and side covering portion 4E.No It is same as intermediate coat 11, in intermediate coat 11E, 2 sides only opposite are by side covering portion 4E packet in 4 sides of first layer 1E Cover (right side and left side of Fig. 6).The material of side covering portion 4E is different from the material of second layer 2E and third layer 3E.Side cladding Portion 4E is formed from second layer 2E and third layer 3E by different resin combinations.With being different from second layer 2E and third layer 3E, Additionally constitute side covering portion 4E.Opposite 2 side in 4 sides of first layer 1E is not by side covering portion 4E packet It covers but exposes (the nearby side and inboard of Fig. 6).Side covering portion 4E is also coated with the side of second layer 2E and third layer 3E Portion.
Fig. 7 is the perspective view for schematically showing the intermediate film for laminated glasses of the 7th embodiment of the invention.
Intermediate coat 11F shown in Fig. 7 is the multilayer intermediate coat with double-layer structure.The flat shape of intermediate coat 11F is four Side shape.
Intermediate coat 11F has first layer 1F and second layer 2F.Intermediate coat 11F has side covering portion 4F.
First layer 1F has opposite the 1st interarea and the 2nd interarea.First layer 1F has the 1st interarea of connection and the 2nd interarea Side.In the present embodiment, side is planar, as side.First layer 1F has 4 sides.
Side covering portion 4F is coated with the entirety of opposite 2 side in 4 sides of first layer 1F.Specifically, 2 sides only opposite coat (right side and left side of Fig. 7) by side covering portion 4F in 4 sides of first layer 1F.By Two layers of 2F and third layer 3F constitute side covering portion 4F.It is not wrapped by side opposite 2 side in 4 sides of first layer 1F It covers portion 4F cladding but exposes (the nearby side and inboard of Fig. 7).It should be noted that the 2nd interarea of first layer 1F also exposes. It can lamination laminated glass member on the 2nd interarea of first layer 1F.
Fig. 8 is the perspective view for schematically showing the intermediate film for laminated glasses of the 8th embodiment of the invention.
Intermediate coat 11G shown in Fig. 8 has first layer 1G and second layer 2G.Intermediate coat 11G has side covering portion 4G.No Be same as intermediate coat 11, in intermediate coat 11G, in 4 sides of first layer 1G only 1 side by side covering portion 4G coat (Fig. 8 Left side).Side covering portion 4G is made of second layer 2G.3 sides in 4 sides of first layer 1G are not by side covering portion 4G is coated but is exposed (nearby side, inboard and the right side of Fig. 8).It should be noted that the 2nd interarea of first layer 1G also reveals Out.It can lamination such as laminated glass member on the 2nd interarea of first layer 1G.
Fig. 9 is the perspective view for schematically showing the intermediate film for laminated glasses of the 9th embodiment of the invention.
Intermediate coat 11H shown in Fig. 9 is the single layer intermediate coat with 1 layer of structure.The flat shape of intermediate coat 11H is four sides Shape.
Intermediate coat 11H has first layer 1H and side covering portion 4H.
First layer 1H has opposite the 1st interarea and the 2nd interarea.First layer 1H has the 1st interarea of connection and the 2nd interarea Side.In the present embodiment, side is planar, as side.First layer 1H has 4 sides.
Side covering portion 4H is coated with the entire side of first layer 1H.Specifically, 4 side entirety quilts of first layer 1H Side covering portion 4H cladding.It should be noted that the 1st interarea of first layer 1H and the 2nd interarea also expose.The of first layer 1H It can lamination such as laminated glass member on 1 interarea and the 2nd interarea.
Figure 10 is the perspective view for schematically showing the intermediate film for laminated glasses of the 10th embodiment of the invention.
Intermediate coat 11I shown in Fig. 10 has first layer 1I and side covering portion 4I.
Different from intermediate coat 11, in intermediate coat 11I, 2 sides only opposite are by side in 4 sides of first layer 1I Covering portion 4I coats (right side and left side of Figure 10).It is not wrapped by side opposite 2 side in 4 sides of first layer 1I It covers portion 4I cladding but exposes (the nearby side and inboard of Figure 10).It should be noted that the 1st interarea of first layer 1I and the 2nd Interarea also exposes.It can lamination such as laminated glass member on the 1st interarea of first layer 1I and the 2nd interarea.
Figure 11 is the perspective view for schematically showing the intermediate film for laminated glasses of the 11st embodiment of the invention.
Intermediate coat 11J shown in Figure 11 has first layer 1J and side covering portion 4J.
Different from intermediate coat 11, in intermediate coat 11J, in 4 sides of first layer 1J only 1 side by side covering portion 4J coats (left side of Figure 11).3 sides in 4 sides of first layer 1J are not coated by side covering portion 4J but are exposed (nearby side, inboard and the right side of Figure 11).It should be noted that the 1st interarea of first layer 1J and the 2nd interarea also expose. It can lamination such as laminated glass member on the 1st interarea of first layer 1J and the 2nd interarea.
As embodiment described above, as long as above-mentioned side covering portion is coated with the above-mentioned side of above-mentioned first layer at least A part.If above-mentioned side covering portion is coated at least part of the above-mentioned side of above-mentioned first layer, exist The region of above-mentioned side covering portion, can make end be not likely to produce foaming.There are the region of above-mentioned side covering portion is bigger, can make The region that foaming is not likely to produce is bigger.Above-mentioned side covering portion can be coated with the portion for being equivalent to above-mentioned side of above-mentioned first layer The entire periphery divided, can also be coated with the portion perimeter of the part for being equivalent to above-mentioned side of above-mentioned first layer.
In the case where constituting above-mentioned resin covering portion by the above-mentioned second layer, by making the above-mentioned second layer extend to above-mentioned At least part of one layer of above-mentioned side and at least part of the above-mentioned side that is coated with above-mentioned first layer.By upper In the case where stating the above-mentioned resin covering portion of third layer composition, by making above-mentioned third layer extend to the above-mentioned side of above-mentioned first layer At least part and be coated at least part of the above-mentioned side of above-mentioned first layer.
From the viewpoint of further suppressing the foaming of end, further suppressing plate offset, as above-mentioned first layer In 1 week distance 100% of the above-mentioned side of periphery, the distance for the side being coated with by above-mentioned side covering portion is preferably 5% More than, more preferably 10% or more, further preferably 15% or more, further preferably 20% or more, especially preferably 25% or more, additionally, it is preferred that being 100% or less.
From the viewpoint of further suppressing the foaming of end, further suppressing plate offset, in the above-mentioned of above-mentioned first layer In the total surface area 100% of side, the surface area being coated with by above-mentioned side covering portion is preferably 5% or more, more preferably 10% or more, further preferably 15% or more, further preferably 20% or more, especially preferably 25% or more, in addition, excellent It is selected as 100% or less.
In the case where the flat shape of above-mentioned intermediate coat is the polygons such as quadrangle, preferably more than 1 side of first layer Side is coated by above-mentioned side covering portion, and sides more than 2 sides of more preferable first layer is coated by above-mentioned side covering portion.From into From the perspective of one step inhibits the foaming of end, further suppresses plate offset, sides more than 3 sides of further preferred first layer It is coated by above-mentioned side covering portion, the side on 4 sides of particularly preferred first layer is coated by above-mentioned side covering portion.
From the viewpoint of further suppressing the foaming of end, further suppressing plate offset, the thickness of above-mentioned side covering portion Degree is preferably 0.05mm or more, more preferably 0.06mm or more, further preferably 0.07mm or more.From making mentioning for sound-proofing From the perspective of the inhibitory effect balance of high, end foaming inhibition and plate offset improves well, above-mentioned side covering portion Thickness be preferably 2mm hereinafter, more preferably 1.8mm or less.The thickness of side covering portion can be by by the side of above-mentioned first layer The thickness of side covering portion in portion is averaged and is found out.In the thickness of side covering portion, not by not formed side covering portion Part take into account.
From the viewpoint of further suppressing the foaming of end, further suppressing plate offset, intermediate coat of the invention is preferred Has the above-mentioned second layer on above-mentioned 1st interarea for being set to above-mentioned first layer.
From the viewpoint of further suppressing the foaming of end, further suppressing plate offset, preferably above-mentioned first layer exists Modulus of shearing at 25 DEG C is 0.17MPa hereinafter, and modulus of shearing of the above-mentioned second layer at 25 DEG C is more than 1MPa.
From the viewpoint of further suppressing the foaming of end, further suppressing plate offset, the above-mentioned second layer is at 25 DEG C Modulus of shearing be preferably 3MPa or more, more preferably 5MPa or more.Modulus of shearing of the above-mentioned second layer at 25 DEG C can be 100MPa or less.
From the viewpoint of further suppressing the foaming of end, further suppressing plate offset, intermediate coat of the invention is preferred Has the above-mentioned third layer on above-mentioned 2nd interarea for being set to above-mentioned first layer.
From the viewpoint of further suppressing the foaming of end, further suppressing plate offset, preferably above-mentioned first layer is 25 Modulus of shearing at DEG C is 0.17MPa hereinafter, and modulus of shearing of the above-mentioned third layer at 25 DEG C is more than 1MPa.
From the viewpoint of further suppressing the foaming of end, further suppressing plate offset, above-mentioned third layer is at 25 DEG C Modulus of shearing be preferably 3MPa or more, more preferably 5MPa or more.Modulus of shearing of the above-mentioned third layer at 25 DEG C can be 100MPa or less.
Hereinafter, to the above-mentioned first layer, the above-mentioned second layer, above-mentioned third layer and the above-mentioned side that constitute intermediate coat of the invention Include in the details of portion's covering portion and above-mentioned first layer, the above-mentioned second layer, above-mentioned third layer and above-mentioned side covering portion The details of each ingredient are illustrated.
(resin)
Above-mentioned first layer, the above-mentioned second layer, above-mentioned third layer and above-mentioned side covering portion preferably comprise resin respectively.On Can be used only by stating resin by a kind, also can be used in combination two or more.
As above-mentioned resin, thermosetting resin and thermoplastic resin can be enumerated.Above-mentioned resin is also possible to make photocuring Solidfied material made of property compound or moisture-curable compound cures.It is above-mentioned to make photocurable compound or moisture-curable Close solidfied material made of object solidification is also thermoplastic resin sometimes.
It should be noted that so-called thermoplastic resin, refers to and occur to soften if being heated and show plasticity, such as Fruit is cooled to room temperature, the resin solidified.So-called thermoplastic elastomer (TPE) refers in thermoplastic resin especially under heating It can occur to soften and show plasticity, be cooled to room temperature the resin that (25 DEG C) then occur solidification and show caoutchouc elasticity.
It as above-mentioned thermoplastic resin, can enumerate: polyvinyl acetal resin, polyester resin, aliphatic poly alkene, polyphenyl Ethylene, ethylene-acrylic acid copolymer resin, polyurethane resin, ionomer resin, gathers ethylene-vinyl acetate copolymer resin Vinyl alcohol resin and polyvinyl acetate etc..The thermoplastic resin other than these can also be used.It should be noted that polyformaldehyde Resin is included in polyvinyl acetal resin.
Foregoing illustrative thermoplastic resin can become thermoplastic elastic by adjusting molecular structure, degree of polymerization of resin etc. Body.
Above-mentioned resin is preferably thermoplastic resin, more preferably polyvinyl acetal resin, polyester resin or poly- acetic acid second Enester, further preferably polyvinyl acetal resin or polyester resin, above-mentioned polyvinyl acetal resin are especially preferably poly- Vinyl butyral resin.
Above-mentioned first layer preferably comprises thermoplastic resin (hereinafter sometimes referred to as thermoplastic resin (1)) or comprising making light Solidfied material made of curability compound or moisture-curable compound cures (hereinafter sometimes referred to as solidfied material (1)).It will be hot Plastic resin (1) and solidfied material (1) are referred to as resin (1).Above-mentioned first layer may include thermoplastic resin (1), can also be with Comprising making solidfied material made of photocurable compound or moisture-curable compound cures.Above-mentioned first layer preferably comprises poly- second Enol acetal resin (hereinafter sometimes referred to as polyvinyl acetal resin (1)) or polyester resin (hereinafter sometimes referred to as polyester Resin (1)) it is used as thermoplastic resin (1).The above-mentioned second layer preferably comprises thermoplastic resin (hereinafter sometimes referred to as thermoplastic resin Rouge (2)).The above-mentioned second layer preferably comprises polyvinyl acetal resin (hereinafter sometimes referred to as polyvinyl acetal resin (2)) As thermoplastic resin (2).Above-mentioned third layer preferably comprises thermoplastic resin (hereinafter sometimes referred to as thermoplastic resin (3)). Above-mentioned third layer preferably comprises polyvinyl acetal resin (hereinafter sometimes referred to as polyvinyl acetal resin (3)) as thermoplastic Property resin (3).Above-mentioned resin covering portion preferably comprises resin (hereinafter sometimes referred to as resin (4)), preferably comprises thermoplastic resin Rouge (hereinafter sometimes referred to as thermoplastic resin (4)) is used as resin (4).Above-mentioned resin covering portion preferably comprises Pioloform, polyvinyl acetal Resin (hereinafter sometimes referred to as polyvinyl acetal resin (4)), epoxy resin (hereinafter sometimes referred to as epoxy resin (4)), Polyester resin (hereinafter sometimes referred to as polyester resin (4)) or acrylic resin (hereinafter sometimes referred to as epoxy resin (4)) As resin (4).Above-mentioned thermoplastic resin (1), above-mentioned thermoplastic resin (2), above-mentioned thermoplastic resin (3), above-mentioned resin (4) And above-mentioned thermoplastic resin (4) can be used only a kind respectively, also can be used in combination two or more.Above-mentioned thermoplastic resin (1), on Stating thermoplastic resin (2), above-mentioned thermoplastic resin (3) and above-mentioned thermoplastic resin (4) can be the same or different.
Photocurable compound or moisture-curable compound are preferably the curability chemical combination with (methyl) acryloyl group Object, more preferably (methyl) acrylic polymer.Above-mentioned resin is preferably the curability chemical combination with (methyl) acryloyl group Object, more preferably (methyl) acrylic polymer.
Above-mentioned (methyl) acrylic polymer preferably includes the curability compound with (methyl) acryloyl group The polymer of polymerizable composition, polymerizable composition.Above-mentioned polymerizable composition, polymerizable composition includes polymeric composition.It include above-mentioned solidification to be effectively formed Above-mentioned solidfied material in the layer of object can also make in above-mentioned polymerizable composition, polymerizable composition comprising photoreaction initiator.Above-mentioned polymerism group The auxiliary agent to promote curing reaction can be included while comprising photoreaction initiator by closing object.There is (methyl) as above-mentioned The typical example of the curability compound of acryloyl group can enumerate (methyl) acrylate.Above-mentioned (methyl) acrylic polymer Preferably poly- (methyl) acrylate.
In order to effectively obtain effect of the invention, above-mentioned polymeric composition is preferably comprised: having (the first of cyclic annular ether structure Base) acrylate, (methyl) acrylate with aromatic ring, (methyl) acrylate, side chain carbon with polar group Number is 6 non-ring type (methyl) acrylate below.By using these preferred (methyl) acrylate, can balance it is good Sound-proofing and foaming rejection are improved simultaneously in ground.
As above-mentioned (methyl) acrylate with cyclic annular ether structure, can enumerate: (methyl) glycidyl acrylate, (methyl) acrylic acid 2- hydroxy methacrylate glycidol ether, (methyl) acrylic acid 3- hydroxy propyl ester glycidol ether, acrylic acid 4- hydroxyl The own ester of base butyl ester glycidol ether, (methyl) acrylic acid 5- hydroxyl pentyl ester glycidol ether, (methyl) acrylic acid 6- hydroxyl shrinks Glycerin ether；(methyl) acrylic acid (3- methy oxetane -3- base) methyl esters, (methyl) acrylic acid (3- propyl oxetanes - 3- yl) methyl esters, (methyl) acrylic acid (3- Ethyloxetane -3- base) methyl esters, (methyl) acrylic acid (3- butyl oxa- ring fourth Alkane -3- base) methyl esters, (methyl) acrylic acid (3- Ethyloxetane -3- base) ethyl ester, (methyl) acrylic acid (3- ethyl oxa- Cyclobutane -3- base) propyl ester, (methyl) acrylic acid (3- Ethyloxetane -3- base) butyl ester, (methyl) acrylic acid (3- ethyl Oxetanes -3- base) pentyl ester, (methyl) acrylic acid (3- Ethyloxetane -3- base) own ester；(methyl) acrylic acid tetrahydro Chaff ester, gamma-butyrolacton (methyl) acrylate, (methyl) acrylic acid (2,2- dimethyl -1,3- dioxolane -4- base) first Ester, (methyl) acrylic acid (2- methyl -2- ethyl -1,3- dioxolane -4- base) methyl esters, (methyl) acrylic acid (2- methyl - 2- isobutyl group -1,3- dioxolane -4- base) methyl esters, (methyl) acrylic acid (2- cyclohexyl -1,3- dioxolane -4- Base) methyl esters, tetrahydrofurfuryl alcohol acrylic polymer ester；(methyl) acrylic acid tetrahydro -2H- pyrans -2- base ester, (methyl) acrylic acid 2- { 1- [(tetrahydro -2H- pyrans -2- base) oxygroup] -2- methyl-propyl } ester, cyclic trimethylolpropane dimethoxym ethane acrylate, (first Base) acryloyl morpholine etc..From the viewpoint of effectively obtaining effect of the invention, especially preferably (methyl) acrylic acid tetrahydro Chaff ester, cyclic trimethylolpropane dimethoxym ethane acrylate.
It as above-mentioned (methyl) acrylate with aromatic ring, can enumerate: benzyl acrylate, phenoxy group polyethylene glycol propylene Acid esters etc..
As above-mentioned (methyl) acrylate with polar group, can enumerate with hydroxyl, amide groups, amino, isocyanide (methyl) acrylate as polar group such as perester radical.
It as (methyl) acrylate with hydroxyl, such as can enumerate: (methyl) acrylic acid 2- hydroxy methacrylate, (methyl) Hydroxypropyl acrylate etc..
It as (methyl) acrylate with amide groups, such as can enumerate: N, N- dimethylaminopropyl (methyl) third Acrylamide, N, N- dimethyl (methyl) acrylamide, (methyl) acryloyl morpholine, N- isopropyl (methyl) acrylamide, N- hydroxyl Base ethyl (methyl) acrylamide etc..
It as (methyl) acrylate with amide groups or amino, such as can enumerate: N- dialkyl aminoalkyl (first Base) acrylamide, N, N- dialkyl aminoalkyl (methyl) acrylamide etc..
As (methyl) acrylate with isocyanate group, can enumerate: triallyl isocyanurate and its derivative Deng.
Above-mentioned (methyl) acrylate can be the multi-carboxylate with (methyl) acryloyl group.There is (first as this Base) acryloyl group multi-carboxylate, succinic acid 2- acryloyloxyethyl ester etc. can be enumerated.
From the viewpoint of effectively obtaining effect of the invention, it is however preferred to have (methyl) acrylate of hydroxyl, especially It is preferably (methyl) acrylic acid 2- hydroxy methacrylate, (methyl) hydroxypropyl acrylate.
It is 6 non-ring type (methyl) acrylate below as above-mentioned side chain carbon number, such as can enumerates: (methyl) third E pioic acid methyl ester, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate.
In order to effectively obtain effect of the invention, in above-mentioned 100 weight % of polymeric composition, side chain carbon number is 8 The combined amount of above non-ring type (methyl) acrylate is preferably shorter than 20 weight %.
As above-mentioned (methyl) acrylate, in addition to above compound, such as can enumerate: diethylene glycol monoethyl ether (first Base) acrylate, (methyl) isobornyl acrylate, (methyl) acrylic acid 3- methoxybutyl, phthalic acid 2- acryloyl Oxygroup ethyl -2- hydroxy propyl ester, phthalic acid 2- acryloyl-oxyethyl -2- hydroxy propyl ester, (methyl) cyclohexyl acrylate； Ethylene glycol two (methyl) acrylate, diethylene glycol two (methyl) acrylate, tetraethylene glycol two (methyl) acrylate, 1,6- Hexylene glycol two (methyl) acrylate, 1,9- nonanediol two (methyl) acrylate, polytetramethylene glycol two (methyl) propylene Acid esters, neopentyl glycol two (methyl) acrylate, 1,3 butylene glycol two (methyl) acrylate, the bis- [4- (acryloxies of 2,2- Ethyoxyl) phenyl] propane two (methyl) acrylate；Trimethylolpropane tris (methyl) acrylate, three (first of pentaerythrite Base) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, tricresyl phosphate (2- acryloyl-oxyethyl) ester, tetramethylol methane three (methyl) acrylate, four hydroxyl first (methyl) acrylate of base propane four and its derivative etc..
Above-mentioned (methyl) acrylate can be used only a kind, two or more can also be applied in combination.Above-mentioned (methyl) acrylic acid Quasi polymer can be the homopolymer of above-mentioned (methyl) acrylate, be also possible to the polymerization comprising above-mentioned (methyl) acrylate The copolymer of ingredient.
It is specific enumerable as above-mentioned photoreaction initiator: 2- methyl-1-(4- methyl mercapto phenyl)-2- morpholinopropane- 1- ketone, 2- benzyl -2- dimethylamino -1- (4- morpholino phenyl)-butanone -1,2- (dimethylamino) -2- [(4- methylbenzene Base) methyl] -1- [4- (4- morpholinyl) phenyl] -1- butanone, 2,4,6- trimethylbenzoy-dipheny-phosphine oxide, it is bis- (2, 4,6- trimethylbenzoyl)-phenyl phosphine oxide, bis- (η 5-2,4- cyclopentadiene -1- bases)-bis- (bis- fluoro- 3- (1H- pyrroles of 2,6- Cough up-1- base)-phenyl) titanium, 2- methyl-1-(4- methyl mercapto phenyl)-2- morpholinopropane-1- ketone, 2- benzyl-2- dimethylamino Base -1- (4- morpholino phenyl)-butanone -1,2- (dimethylamino) -2- [(4- aminomethyl phenyl) methyl] -1- [4- (4- morpholine Base) phenyl] -1- butanone, diethoxy acetophenone, 2- hydroxy-2-methyl -1- phenyl-propane -1- ketone, benzoin dimethylether, 4- (2- hydroxyl-oxethyl) phenyl-(2- hydroxyl -2- propyl) ketone, 1- hydroxycyclohexylphenylketone, 2- methyl -2- morpholinyl (4- sulphur For aminomethyl phenyl) propane -1- ketone, 2- benzyl -2- dimethylamino -1- (4- morpholino phenyl) butanone, 2- hydroxy-2-methyl - 1- [4- (1- methyl ethylene) phenyl] acetone oligomer, benzoin, benzoin methylether, benzoin ethyl ether, benzoin iso-propylether, Benzoin isobutyl ether, benzophenone, methyl o-benzoylbenzoate, 4- phenyl benzophenone, 4- benzoyl -4'- methyl-two Diphenyl sulfide, 3,3', 4,4'- tetra- (tert-butyl hydroperoxide carbonyl) benzophenone, 2,4,6- tri-methyl benzophenone, 4- benzoyl Base-N, N- dimethyl-N-[2- (1- oxo -2- acrylic oxygroup) ethyl] benzene first ammonium bromide, (4- benzoylbenzyl) three Ammonio methacrylate, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4- diethyl thioxanthone, bis- clopenthixal ketone of 2,4-, 1- Chloro- 4- propoxythioxanthone, 2- (3- dimethylamino -2- hydroxyl) -3,4- dimethyl -9H- thioxanthones -9- ketone meso chlorination Object, 2,4,6- trimethylbenzoy-dipheny phosphine oxide, bis- (2,6- Dimethoxybenzoyl) -2,4,4- trimethyls-penta Base phosphine oxide, bis- (2,4,6- trimethylbenzoyl)-phenyl phosphine oxides, triphen carbonFour (pentafluorophenyl group) borates etc..On Can be used only by stating photoreaction initiator by a kind, also can be used in combination two or more.
As above-mentioned auxiliary agent, can enumerate: triethanolamine, triisopropanolamine, 4,4'- dimethylamino benzophenone (rice its Strangle ketone), 4,4'- diethylamino benzophenone, 2- dimethyl amino benzoate, ethyl 4-dimethylaminobenzoate. In addition, can enumerate: 4- dimethylaminobenzoic acid (n-butoxy) ethyl ester, 4- dimethylaminobenzoic acid isopentyl ester, 4- diformazan Base aminobenzoic acid 2- ethylhexyl, 2,4- diethyl thioxanthone, 2,4- diisopropylthioxanthone etc..Above-mentioned auxiliary agent can be used only 1 kind, it also can be used in combination two or more.
Above-mentioned auxiliary agent is preferably benzoin dimethylether, 1- hydroxycyclohexylphenylketone, benzoyl isopropyl ether, 4- (2- hydroxyl Base oxethyl)-phenyl (2- hydroxyl -2- propyl) ketone, 2- hydroxy-2-methyl -1- phenyl-propane -1- ketone, triphen carbonFour (five fluorine Phenyl) borate.
In above-mentioned 100 weight % of polymerizable composition, polymerizable composition, the content of above-mentioned photoreaction initiator is preferably 0.01 weight % More than, more than more preferably 0.1 parts by weight, additionally, it is preferred that being 10 weight % hereinafter, more preferably 5 weight % or less.If above-mentioned The content of photoreaction initiator be above-mentioned lower limit more than and the above-mentioned upper limit hereinafter, then photo-curable and storage stability are further It improves.
From excellent effect aspect of the invention, above-mentioned polyvinyl acetate preferably includes vinyl acetate and tool There is the polymer of the polymerizable composition, polymerizable composition of the monomer of above-mentioned functional group.
As the monomer with above-mentioned functional group, can enumerate: 3- methyl -3- butyl 1- alcohol, ethylene glycol monovinyl ether, with And N-isopropylacrylamide etc..
From the viewpoint of effectively improving sound-proofing, the weight average molecular weight of polyvinyl acetate is preferably 250,000 or more, More preferably 300,000 or more, further preferably 400,000 or more, especially preferably 500,000 or more.From making layers cementing power become good From the perspective of good, the weight average molecular weight of polyvinyl acetate is preferably 1,200,000 hereinafter, more preferably 900,000 or less.
Above-mentioned weight average molecular weight indicates the dividing equally again with polystyrene conversion measured by gel permeation chromatography (GPC) Son amount.
The method for polymerizeing above-mentioned polymerizable composition, polymerizable composition and synthesizing above-mentioned polyvinyl acetate is not particularly limited.As this Synthetic method can be enumerated: solution polymerization process, suspension polymerization and UV polymerization etc..
From the transparency for improving intermediate coat and so that the transparency is improved the sound-proofing and layers cementing of intermediate coat From the perspective of power effectively improves, the synthetic method of above-mentioned polyvinyl acetate is preferably solution polymerization process.
Above-mentioned polyvinyl acetal resin for example can be by being obtained polyvinyl alcohol (PVA) progress acetalation using aldehyde. Above-mentioned polyvinyl acetal resin is preferably the acetal compound of polyvinyl alcohol.Above-mentioned polyvinyl alcohol for example can be by by poly- acetic acid second Enester, which is saponified, to be obtained.The saponification degree of above-mentioned polyvinyl alcohol is generally 70~99.9 moles of %.
The average degree of polymerization of above-mentioned polyvinyl alcohol (PVA) is preferably 200 or more, and more preferably 500 or more, further preferably It is 1500 or more, further preferably 1600 or more, especially preferably 2600 or more, most preferably 2700 or more, additionally, it is preferred that For 5000 hereinafter, more preferably 4000 hereinafter, further preferably 3500 or less.If above-mentioned average degree of polymerization be above-mentioned lower limit with On, then the penetration resistance of laminated glass further increases.If above-mentioned average degree of polymerization be the above-mentioned upper limit hereinafter, if intermediate coat at Shape becomes easy.
The average degree of polymerization of above-mentioned polyvinyl alcohol can pass through the method according to JIS K6726 " polyvinyl alcohol test method " It finds out.
The carbon atom number of acetal radical in above-mentioned polyvinyl acetal resin is preferably 3~5, preferably 4 or 5.
It is generally suitable for the aldehyde for the use of carbon atom number being 1~10 as above-mentioned aldehyde.It is 1~10 as above-mentioned carbon atom number Aldehyde, such as can enumerate: formaldehyde, acetaldehyde, propionic aldehyde, n-butanal, isobutylaldehyde, valeraldehyde, 2- ethyl butyraldehyde, n-hexyl aldehyde, n-octaldehyde, just Aldehyde C-9, n-capric aldehyde and benzaldehyde etc..Preferably acetaldehyde, propionic aldehyde, n-butanal, isobutylaldehyde, n-hexyl aldehyde or valeraldehyde, more preferably Acetaldehyde, propionic aldehyde, n-butanal, isobutylaldehyde or valeraldehyde, further preferably n-butanal or valeraldehyde.Above-mentioned aldehyde can be used only a kind, Also it can be used in combination two or more.
The containing ratio (amount of hydroxyl groups) of the hydroxyl of above-mentioned polyvinyl acetal resin (1) is preferably 17 moles of % or more, more excellent It is selected as 20 moles of % or more, further preferably 22 moles of % or more.The hydroxyl of above-mentioned polyvinyl acetal resin (1) contains Rate (amount of hydroxyl groups) be preferably 30 moles of % hereinafter, more preferably 28 moles of % hereinafter, further preferably 27 moles of % hereinafter, into One step is preferably 25 moles of % hereinafter, particularly preferably lower than 25 moles of %, most preferably 24 moles of % or less.If above-mentioned hydroxyl Containing ratio is above-mentioned lower limit or more, then the mechanical strength of intermediate coat further increases.If especially above-mentioned Pioloform, polyvinyl acetal tree The containing ratio of the hydroxyl of rouge (1) is 20 moles of % or more, then reaction efficiency is high and productivity is excellent, in addition, if 30 moles of % Hereinafter, then the sound-proofing of laminated glass further increases, if 28 moles of % hereinafter, then sound-proofing further improves.In addition, If above-mentioned hydroxyl containing ratio be the above-mentioned upper limit hereinafter, if the flexibility of intermediate coat get higher, be easy to handle intermediate coat.
Above-mentioned polyvinyl acetal resin (2), above-mentioned polyvinyl acetal resin (3) and above-mentioned Pioloform, polyvinyl acetal tree Each containing ratio of the hydroxyl of rouge (4) is preferably 25 moles of % or more, more preferably 28 moles of % or more, more preferably 30 moles of % More than, further preferred more than 31 moles %.Above-mentioned polyvinyl acetal resin (2) and above-mentioned polyvinyl acetal resin (3) each containing ratio of hydroxyl is more preferably 31.5 moles of % or more, is even more preferably 32 moles of % or more, especially Preferably 33 moles of % or more.The hydroxyl of above-mentioned polyvinyl acetal resin (2) and above-mentioned polyvinyl acetal resin (3) Each containing ratio is preferably 37 moles of % hereinafter, more preferably 36.5 moles of % are hereinafter, further preferably 36 moles of % or less.If The containing ratio of above-mentioned hydroxyl is above-mentioned lower limit or more, then the bonding force of intermediate coat further increases.In addition, if above-mentioned hydroxyl contains Having rate is the above-mentioned upper limit hereinafter, then the flexibility of intermediate coat is got higher, and is easy to handle intermediate coat.
From the viewpoint of further increasing sound-proofing, the containing ratio of the hydroxyl of above-mentioned polyvinyl acetal resin (1) is excellent Containing ratio of the choosing lower than the hydroxyl of above-mentioned polyvinyl acetal resin (2).It is above-mentioned from the viewpoint of further increasing sound-proofing The containing ratio of the hydroxyl of polyvinyl acetal resin (1) is preferably shorter than containing for the hydroxyl of above-mentioned polyvinyl acetal resin (3) Rate.The containing ratio of the hydroxyl of above-mentioned polyvinyl acetal resin (1) is preferably shorter than the hydroxyl of above-mentioned polyvinyl acetal resin (4) Containing ratio.From the viewpoint of further increasing sound-proofing, the containing ratio of the hydroxyl of above-mentioned polyvinyl acetal resin (1) with The absolute value of the difference of the containing ratio of the hydroxyl of above-mentioned polyvinyl acetal resin (2) is preferably 1 mole of % or more, and more preferably 5 Mole % or more, further preferably 9 moles of % or more, especially preferably 10 moles of % or more, most preferably 12 moles of % with On.From the viewpoint of further increasing sound-proofing, the containing ratio of the hydroxyl of above-mentioned polyvinyl acetal resin (1) gathers with above-mentioned The absolute value of the difference of the containing ratio of the hydroxyl of vinyl acetal resin (3) is preferably 1 mole of % or more, more preferably 5 moles of % More than, further preferably 9 moles of % or more, especially preferably 10 moles of % or more, most preferably 12 moles of % or more.From into From the perspective of one step improves sound-proofing, the containing ratio and above-mentioned polyvinyl alcohol of the hydroxyl of above-mentioned polyvinyl acetal resin (1) The absolute value of the difference of the containing ratio of the hydroxyl of acetal resin (4) is preferably 1 mole of % or more, more preferably 5 moles of % or more, into One step is preferably 9 moles of % or more, especially preferably 10 moles of % or more, most preferably 12 moles of % or more.Above-mentioned polyethylene The difference of the containing ratio of the hydroxyl of the containing ratio and above-mentioned polyvinyl acetal resin (2) of the hydroxyl of acetal resin (1) it is absolute Value is preferably 20 moles of % or less.The containing ratio and above-mentioned Pioloform, polyvinyl acetal of the hydroxyl of above-mentioned polyvinyl acetal resin (1) The absolute value of the difference of the containing ratio of the hydroxyl of resin (3) is preferably 20 moles of % or less.Above-mentioned polyvinyl acetal resin (1) The absolute value of the difference of the containing ratio of the containing ratio of hydroxyl and the hydroxyl of above-mentioned polyvinyl acetal resin (4) is preferably 20 moles of % Below.
The containing ratio of the hydroxyl of above-mentioned polyvinyl acetal resin is will be with the ethylidene amount that hydroxyl is bonded divided by main chain Whole ethylidene amounts calculated by mole fraction value expressed as a percentage.The ethylidene amount that above-mentioned hydroxyl is bonded for example may be used It is measured according to JIS K6728 " polyvinyl butyral test method ".
The degree of acetylation (acetyl base unit weight) of above-mentioned polyvinyl acetal resin (1) is preferably 0.01 mole of % or more, more excellent It is selected as 0.1 mole of % or more, further preferably 7 moles of % or more, further preferably 9 moles of % or more, additionally, it is preferred that being 30 moles of % hereinafter, more preferably 25 moles of % hereinafter, further preferably 24 moles of % hereinafter, especially preferably 20 moles of % Below.If above-mentioned degree of acetylation is above-mentioned lower limit or more, the compatibility of polyvinyl acetal resin and plasticizer is got higher.On if Stating degree of acetylation is the above-mentioned upper limit hereinafter, then the moisture-proof of intermediate coat and laminated glass is got higher.Especially if above-mentioned poly- second The degree of acetylation of enol acetal resin (1) is 0.1 mole of % or more and 25 mole of % hereinafter, then penetration resistance is more excellent.
Above-mentioned polyvinyl acetal resin (2), above-mentioned polyvinyl acetal resin (3) and above-mentioned Pioloform, polyvinyl acetal tree Each degree of acetylation of rouge (4) is preferably 0.01 mole of % or more, more preferably 0.5 mole of % or more, additionally, it is preferred that rubbing for 10 That % is hereinafter, more preferably 2 moles of % or less.If above-mentioned degree of acetylation is above-mentioned lower limit or more, polyvinyl acetal resin It is got higher with the compatibility of plasticizer.If above-mentioned degree of acetylation be the above-mentioned upper limit hereinafter, if the moisture-proof of intermediate coat and laminated glass Property is got higher.
Above-mentioned degree of acetylation is will be calculated by whole ethylidene amounts of the ethylidene amount that acetyl group is bonded divided by main chain Mole fraction value expressed as a percentage.The ethylidene amount that above-mentioned acetyl group is bonded for example can be according to JIS K6728 " poly- second Enol butyral test method " and measure.
The acetalizing degree of above-mentioned polyvinyl acetal resin (1) (is contracting fourth in the case where polyvinyl butyral resin Hydroformylation degree) it is preferably 47 moles of % or more, more preferably 60 moles of % or more, additionally, it is preferred that being 85 moles of % hereinafter, more preferably For 80 moles of % hereinafter, further preferably 75 moles of % or less.If above-mentioned acetalizing degree is above-mentioned lower limit or more, polyethylene The compatibility of acetal resin and plasticizer is got higher.If above-mentioned acetalizing degree be the above-mentioned upper limit hereinafter, if to manufacture polyethylene Reaction time needed for acetal resin shortens.
Above-mentioned polyvinyl acetal resin (2), above-mentioned polyvinyl acetal resin (3) and above-mentioned Pioloform, polyvinyl acetal tree Each acetalizing degree (in the case where polyvinyl butyral resin be butyralization degree) of rouge (4) be preferably 55 moles of % with On, more preferably 60 moles of % or more, additionally, it is preferred that being 75 moles of % hereinafter, more preferably 71 moles of % or less.If above-mentioned contracting Hydroformylation degree is above-mentioned lower limit or more, then the compatibility of polyvinyl acetal resin and plasticizer is got higher.If above-mentioned acetalizing degree is The above-mentioned upper limit to the reaction time needed for manufacturing polyvinyl acetal resin hereinafter, then shorten.
Above-mentioned acetalizing degree is found out in the following way.Hydroxyl is subtracted from whole ethylidene amounts of main chain firstly, finding out Value obtained from the ethylidene amount that the ethylidene amount and acetyl group being bonded are bonded.With obtained value divided by the whole of main chain Ethylidene amount and find out mole fraction.It is acetalizing degree by mole fraction value expressed as a percentage.
It should be noted that the containing ratio (amount of hydroxyl groups) of above-mentioned hydroxyl, acetalizing degree (butyralization degree) and acetylation Degree using result measured by the method according to JIS K6728 " polyvinyl butyral test method " preferably as being calculated.But The measurement according to ASTM D1396-92 can also be used.The case where polyvinyl acetal resin is polyvinyl butyral resin Under, containing ratio (amount of hydroxyl groups), above-mentioned acetalizing degree (butyralization degree) and the above-mentioned degree of acetylation of above-mentioned hydroxyl can be by utilizing According to JIS K6728 " polyvinyl butyral test method " method measured by result and calculate.
Above-mentioned polyester resin can be manufactured by the manufacturing method of generally known polyester.Above-mentioned polyester resin can for example lead to Following method manufacture: the method that polyester is obtained by the condensation reaction of polyacid and polyalcohol is crossed, by the alkane for making polyacid The method that base ester obtains polyester with polyalcohol progress ester exchange reaction, makes to urge by the obtained polyester of the above method in polymerization Further it polymerize the method for obtaining polyester in the presence of agent.
It as above-mentioned polyacid, such as can enumerate: terephthalic acid (TPA), M-phthalic acid, phthalic acid, naphthalenedicarboxylic acid etc. Aromatic dicarboxylic acid；The aliphatic dicarboxyl such as succinic acid, glutaric acid, adipic acid, azelaic acid, decanedioic acid, dodecanedioic acid, dimeric dibasic acid Acid；The unsaturated dicarboxylics such as maleic acid (acid anhydride), fumaric acid, dodecenyl succinic anhydride, terpenes-maleic acid addition product；1,4- The alicyclic dicarboxylic acids such as cyclohexane dicarboxylic acid, tetrahydrophthalic acid, hexahydro M-phthalic acid, 1,2- cyclohexene dicarboxylic acid；Partially The carboxylic acids more than ternarys such as benzenetricarboxylic acid (acid anhydride), Pyromellitic Acid (acid anhydride), methylcyclohexene tricarboxylic acids；Bis- (the 4'- hydroxy benzenes of 4,4- Base) valeric acid, the monocarboxylic acids such as 4- mono- (4'- hydroxy phenyl) valeric acid, P-hydroxybenzoic acid etc..
It as above-mentioned polyalcohol, can enumerate: ethylene glycol, propylene glycol (1,2-PD), 1,3-PD, Isosorbide-5-Nitrae-fourth two Alcohol, 1,2- butanediol, 1,3 butylene glycol, 2- methyl-1,3-propanediol, neopentyl glycol, 1,5- pentanediol, 1,6-HD, 3- Methyl-1,5- pentanediol, 2- ethyl -2- butyl -1,3- propylene glycol, 2,4- diethyl -1,5- pentanediol, 1- methyl-1,8- are pungent Glycol, 3- methyl-1,6- hexylene glycol, 4- methyl-1,7- heptandiol, 4- methyl-1,8- ethohexadiol, 4- propyl -1,8- ethohexadiol, The aliphatic diols such as 1,9- nonanediol；The ethers such as diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol Glycol；1,4 cyclohexane dimethanol, 1,3- cyclohexanedimethanol, 1,2- cyclohexanedimethanol, tristane glycol, A Hydrogenated Bisphenol A Equal alicyclic polyols；Polyalcohols the etc. more than ternarys such as trimethylolpropane, trimethylolethane, pentaerythrite.
It as the commercially available product of above-mentioned polyester resin, such as can enumerate: " the elitel UE-3220 " of Unitika company manufacture And " the Elitel UE-3223 " of Unitika company manufacture.
It should be noted that above-mentioned resin covering portion may include that rubber replaces above-mentioned resin.As above-mentioned rubber, it can arrange It lifts: natural rubber, chlorobutadiene acrylic-nitrile rubber, nitrile rubber, butyl rubber, organic silicon rubber, EP rubbers and fluorine rubber Glue etc..It should be noted that in the present specification, the rubber such as natural rubber and synthetic rubber are included in resin.
(plasticizer)
Above-mentioned first layer preferably comprises plasticizer (hereinafter sometimes referred to as plasticizer (1)).The above-mentioned second layer preferably comprises Plasticizer (hereinafter sometimes referred to as plasticizer (2)).Above-mentioned third layer preferably comprises plasticizer (hereinafter sometimes referred to as plasticizer (3)).Above-mentioned side covering portion preferably comprises plasticizer (hereinafter sometimes referred to as plasticizer (4)).By using plasticizer, into And by using polyvinyl acetal resin and plasticizer combinations, the layer comprising polyvinyl acetal resin and plasticizer is to folder The bonding force of layer glass component or other layers is moderately got higher.Above-mentioned plasticizer is not particularly limited.It is above-mentioned plasticizer (1), above-mentioned Plasticizer (2), above-mentioned plasticizer (3) and above-mentioned plasticizer (4) can be the same or different.Above-mentioned plasticizer (1), above-mentioned increasing Can be used only respectively by moulding agent (2), above-mentioned plasticizer (3) and above-mentioned plasticizer (4) by a kind, also can be used in combination two or more.
As above-mentioned plasticizer, can enumerate: organic ester plasticiser such as unitary organic acid esters and multicomponent organic acid ester and Organic phosphoric acids plasticizer such as organic phosphoric acid plasticizer and organic phosphorous acid plasticizer etc..Preferably organic ester plasticiser.Above-mentioned increasing Moulding agent is preferably liquid plasticizer.
As above-mentioned unitary organic acid esters, the diol ester as obtained from the reacting of glycol and unitary organic acid can be enumerated Deng.It as above-mentioned glycol, can enumerate: triethylene glycol, tetraethylene glycol and tripropylene glycol etc..It, can as above-mentioned unitary organic acid It enumerates: butyric acid, isobutyric acid, caproic acid, 2 Ethylbutanoic acid, enanthic acid, caprylic acid, 2 ethyl hexanoic acid, pelargonic acid and capric acid and benzene first Acid etc..
As above-mentioned multicomponent organic acid ester, multicomponent organic acid can be enumerated with carbon atom number 4~8 with linear chain or branched chain knot The ester compounds etc. of the alcohol of structure.It as above-mentioned multicomponent organic acid, can enumerate: phthalic acid, adipic acid, decanedioic acid and nonyl two Acid etc..
It as above-mentioned organic ester plasticiser, can enumerate: triethylene glycol two (2- propionic acid ethyl ester), (the 2- second of triethylene glycol two Base butyrate), triethylene glycol two (2 ethyl hexanoic acid ester), triethylene glycol dicaprylate, two caprylic acid ester of triethylene glycol, three second two The positive heptanoate of alcohol two, the positive heptanoate of tetraethylene glycol two, dibutyl sebacate, dioctyl azelate, dibutyl carbitol (DBC) adipic acid Ester, ethylene glycol two (2 Ethylbutanoic acid ester), 1,3- propylene glycol two (2 Ethylbutanoic acid ester), two (2 Ethylbutanoic acid of 1,4- butanediol Ester), diethylene glycol two (2 Ethylbutanoic acid ester), diethylene glycol two (2 ethyl hexanoic acid ester), two (2 Ethylbutanoic acid of dipropylene glycol Ester), triethylene glycol two (2- ethylpentanoic ester), tetraethylene glycol two (2 Ethylbutanoic acid ester), diethylene glycol dicaprylate, diethyl two Alcohol dibenzoate, dipropylene glycol dibenzoate, dibutyl maleate, adipic acid bis- (2- butoxyethyl group) esters, adipic acid Dibutyl ester, diisobutyl adipate, adipic acid 2,2- Butoxyethoxy ethyl ester, glycol benzoate, adipic acid 1,3- fourth two Alcohol polyester, dihexyl adipate, dioctyl adipate, adipic acid hexyl cyclohexyl, adipic acid heptyl ester are mixed with adipic acid nonyl ester Close object, diisononyl adipate, diisodecyl adipate (DIDA), adipic acid heptyl nonyl ester, tributyl citrate, acetyl citrate The mixture of the modified decanedioic acid alkyd of tributyl, diethyl carbonate, dibutyl sebacate, oil and phosphate and adipate ester Deng.Organic ester plasticiser other than these can also be used.Other adipate esters other than above-mentioned adipate ester can also be used.
It as above-mentioned organic phosphoric acid plasticizer, can enumerate: tributoxyethyl phosphate, isodecyl phenylester, phosphoric acid Front three phenyl ester and tricresyl phosphate isopropyl ester etc..
Above-mentioned plasticizer is preferably two ester plasticisers represented by following formula (11).
[chemical formula 1]
In above-mentioned formula (11), R1 and R2 respectively indicate the organic group of carbon atom number 2~10, and R3 indicates ethylidene, Asia Isopropyl or sub- n-propyl, p indicate 3~10 integer.R1 and R2 in above-mentioned formula (11) be respectively preferably carbon atom number 5~ 10 organic group, the more preferably organic group of carbon atom number 6~10.
Above-mentioned plasticizer preferably comprises triethylene glycol two (2 ethyl hexanoic acid ester) (3GO), two (2 Ethylbutanoic acid of triethylene glycol Ester) (3GH) or triethylene glycol two (2- propionic acid ethyl ester).Above-mentioned plasticizer more preferably includes two (2 ethyl hexanoic acid of triethylene glycol Ester) or triethylene glycol two (2 Ethylbutanoic acid ester), further preferably include triethylene glycol two (2 ethyl hexanoic acid ester).
The content of the above-mentioned plasticizer (1) relative to above-mentioned (1) 100 parts by weight of resin in above-mentioned first layer is set as containing It measures (1).In the case where above-mentioned resin (1) is thermoplastic resin (1), (1) 100 parts by weight of resin are thermoplastic resin (1) 100 parts by weight.In the case where resin (1) is polyvinyl acetal resin (1), (1) 100 parts by weight of resin are polyvinyl alcohol (1) 100 parts by weight of acetal resin.In the case where resin (1) is polyester resin (1), (1) 100 parts by weight of resin are polyester (1) 100 parts by weight of resin.Other resins are also identical.Above-mentioned content (1) is preferably 50 parts by weight or more, more preferably 55 weight Part or more, it is more than further preferably 60 parts by weight, additionally, it is preferred that be 130 parts by weight hereinafter, more preferably 100 parts by weight with Under, further preferably 90 parts by weight are hereinafter, be especially more preferably 85 parts by weight hereinafter, below most preferably 80 parts by weight.If Above-mentioned content (1) is above-mentioned lower limit or more, then the flexibility of intermediate coat is got higher, and is easy to handle intermediate coat.If above-mentioned contain Measuring (1) is the above-mentioned upper limit hereinafter, then the penetration resistance of laminated glass further increases.
By the content of the above-mentioned plasticizer (2) relative to above-mentioned (2) 100 parts by weight of thermoplastic resin in the above-mentioned second layer It is set as content (2).In the case that thermoplastic resin (2) in above-mentioned third layer is polyvinyl acetal resin (2), thermoplasticity (2) 100 parts by weight of resin are (2) 100 parts by weight of polyvinyl acetal resin.It is polyester resin (2) in thermoplastic resin (2) In the case where, (2) 100 parts by weight of thermoplastic resin are (2) 100 parts by weight of polyester resin.The benchmark of other resins is also identical. The content of the above-mentioned plasticizer (3) relative to above-mentioned (3) 100 parts by weight of thermoplastic resin in above-mentioned third layer is set as content (3).In the case where thermoplastic resin (3) are polyvinyl acetal resin (3), (3) 100 parts by weight of thermoplastic resin are poly- (3) 100 parts by weight of vinyl acetal resin.In the case where thermoplastic resin (3) are polyester resin (3), thermoplastic resin (3) 100 parts by weight are (3) 100 parts by weight of polyester resin.The benchmark of other resins is also identical.By the phase in above-mentioned side covering portion Content (4) are set as the content of the above-mentioned plasticizer (4) of above-mentioned (4) 100 parts by weight of resin.It is thermoplastic in above-mentioned resin (4) In the case where property resin (4), (4) 100 parts by weight of resin are 100 parts by weight of thermoplastic resin.It is poly- in thermoplastic resin (4) In the case where vinyl acetal resin (4), (4) 100 parts by weight of thermoplastic resin are (4) 100 weight of polyvinyl acetal resin Measure part.In the case where thermoplastic resin (4) are polyester resin (4), (4) 100 parts by weight of thermoplastic resin are polyester resin (4) 100 parts by weight.The benchmark of other resins is also identical.Above-mentioned content (2), above-mentioned content (3) and above-mentioned content (4) are preferred More than 10 parts by weight, more than more preferably 15 parts by weight, additionally, it is preferred that being 40 parts by weight hereinafter, more preferably 39 parts by weight Hereinafter, further preferably 35 parts by weight hereinafter, even more preferably be 32 parts by weight hereinafter, especially preferably 30 parts by weight with Under.If above-mentioned content (2), above-mentioned content (3) and above-mentioned content (4) are above-mentioned lower limit or more, the flexibility of intermediate coat becomes The processing of height, intermediate coat becomes easy.If above-mentioned content (2), above-mentioned content (3) and above-mentioned content (4) be the above-mentioned upper limit with Under, then penetration resistance further increases.
In order to further increase the sound-proofing of laminated glass, above-mentioned content (1) is preferably greater than above-mentioned content (2), above-mentioned to contain Amount (1) is preferably greater than above-mentioned content (3), and above-mentioned content (1) is preferably greater than above-mentioned content (4).
From the viewpoint of the sound-proofing for further increasing laminated glass, the difference of above-mentioned content (2) and above-mentioned content (1) Absolute value, above-mentioned content (3) and the absolute value of the difference of above-mentioned content (1) and the difference of above-mentioned content (4) and above-mentioned content (1) Absolute value be respectively preferably 10 parts by weight or more, more than more preferably 15 parts by weight, more than further preferably 20 parts by weight. The absolute value of the difference of above-mentioned content (2) and above-mentioned content (1), the absolute value of the difference of above-mentioned content (3) and above-mentioned content (1), with And above-mentioned content (4) and the absolute value of the difference of above-mentioned content (1) are respectively preferably 80 parts by weight hereinafter, more preferably 75 parts by weight Hereinafter, below further preferably 70 parts by weight.
(softening point is 70 DEG C or more and 200 DEG C of compounds below)
From the viewpoint of effectively improving sound-proofing, it is 70 DEG C or more and 200 that above-mentioned first layer, which preferably comprises softening point, DEG C compound (hereinafter sometimes referred to as compound (A)) below., it can be said that by using above compound (A), in first layer Glass transition temperature near molecular motion aggravation, as a result get higher sound-proofing.Above compound (A) can be used only a kind, Also it can be used in combination two or more.
From the viewpoint of effectively improving sound-proofing, the softening point of above compound (A) is preferably 80 DEG C or more, separately Outside, preferably 190 DEG C or less.
It should be noted that in the case where above compound (A) is compound without softening point, from effectively mentioning From the perspective of high sound-proofing, it is 70 DEG C or more and 200 DEG C of compounds below that above-mentioned first layer, which preferably comprises fusing point,.
Above compound (A) is preferably the compound different from thermoplastic resin.Above compound (A) preferably and poly- second The different compound of enol acetal resin.
It is specific enumerable as above compound (A): there are multiple aromatic ester compounds；With multiple aromatic series Ether compound；The tackifier such as rosin resin, terpene resin and Petropols；Chlorinated paraffin etc..
It as the commercially available product of above compound (A), can enumerate: KE-311 (manufacture of Arakawa Chemical Industries company, softening point 95 DEG C) and Enpara 70 (manufacture of Ajinomoto Fine-Techno company, 100 DEG C of softening point) etc..
In above-mentioned 100 weight % of first layer, the content of above compound (A) is preferably 20 weight % or more, more preferably For 30 weight % or more, additionally, it is preferred that being 50 weight % hereinafter, more preferably 40 weight % or less.In addition, relative to above-mentioned heat (1) 100 parts by weight of plastic resin (are polyvinyl alcohol contracting in the case where thermoplastic resin (1) is polyvinyl acetal resin (1) (1) 100 parts by weight of urea formaldehyde) the content of above compound (A) be preferably 50 parts by weight or more, more preferably 60 parts by weight with On, additionally, it is preferred that being 200 parts by weight hereinafter, below more preferably 150 parts by weight.If the content of above compound (A) is above-mentioned More than lower limit, then sound-proofing is effectively got higher.If above compound (A) content be the above-mentioned upper limit hereinafter, if formability become More preferably.
(thermal insulation substance)
Above-mentioned intermediate coat also may include thermal insulation substance (thermal insulation compound).Above-mentioned first layer may include thermal insulation object Matter.The above-mentioned second layer may include thermal insulation substance.Above-mentioned third layer may include thermal insulation substance.Above-mentioned side covering portion may include Thermal insulation substance.Above-mentioned thermal insulation substance can be used only a kind, also can be used in combination two or more.
Ingredient X:
Above-mentioned intermediate coat also may include at least 1 in phthalocyanine compound, naphthols cyanine compound and anthracene phthalocyanine compound Kind ingredient X.Above-mentioned first layer may include mentioned component X.The above-mentioned second layer may include mentioned component X.Above-mentioned third layer may include Mentioned component X.Above-mentioned side covering portion may include mentioned component X.Mentioned component X is thermal insulation substance.Mentioned component X can only make With a kind, two or more also can be used in combination.
Mentioned component X is not particularly limited.As ingredient X, conventionally known phthalocyanine compound, naphthols cyanines chemical combination can be used Object and anthracene phthalocyanine compound.
From the viewpoint of further increasing the thermal insulation of intermediate coat and laminated glass, mentioned component X is preferably selected from phthalein Cyanines, the derivative of phthalocyanine, naphthols cyanines and naphthols cyanines derivative in it is at least one kind of, more preferably phthalocyanine and phthalocyanine spreads out It is at least one kind of in biology.
From the viewpoint of effectively improve thermal insulation and long lasting for higher level keep transmission of visible light, Mentioned component X preferably comprises vanadium atom or copper atom.Mentioned component X preferably comprises vanadium atom, it is also preferred that containing copper atom.It is above-mentioned Ingredient X is more preferably in the derivative of the phthalocyanine containing vanadium atom or copper atom and the phthalocyanine containing vanadium atom or copper atom It is at least one kind of.From the viewpoint of further increasing the thermal insulation of intermediate coat and laminated glass, mentioned component X preferably has in vanadium The structural unit of oxygen atom is bonded on atom.
In position (first layer, the second layer, third layer or side covering portion) 100 weight % comprising mentioned component X, on The content for stating ingredient X is preferably 0.001 weight % or more, more preferably 0.005 weight % or more, further preferably 0.01 weight Measure % or more, especially preferably 0.02 weight % or more.In position (first layer, the second layer, third layer comprising mentioned component X Or side covering portion) in 100 weight %, the content of mentioned component X is preferably 0.2 weight % hereinafter, more preferably 0.1 weight % Hereinafter, further preferably 0.05 weight % is hereinafter, especially preferably 0.04 weight % or less.If the content of mentioned component X is More than above-mentioned lower limit and the above-mentioned upper limit is hereinafter, then thermal insulation is sufficiently got higher, and transmission of visible light is sufficiently got higher.Such as can make can Light-exposed transmissivity reaches 70% or more.
Insulation particle:
Above-mentioned intermediate coat also may include insulation particle.Above-mentioned first layer may include above-mentioned insulation particle.The above-mentioned second layer It may include above-mentioned insulation particle.Above-mentioned third layer may include above-mentioned insulation particle.Above-mentioned side covering portion may include above-mentioned heat-insulated Particle.Above-mentioned insulation particle is thermal insulation substance.By using insulation particle, infrared ray (heat ray) can be effectively shielded.On Can be used only by stating insulation particle by a kind, also can be used in combination two or more.
From the viewpoint of the thermal insulation for further increasing laminated glass, above-mentioned insulation particle is more preferably metal oxide Particle.Above-mentioned insulation particle is preferably formed by particle (metal oxide particle) by the oxide of metal.
Compared with ultraviolet light, the energy that wavelength is greater than the infrared ray of the 780nm or more of visible light is smaller.However, infrared ray Heat effect it is larger, infrared ray be subsequently absorbed in the material after can as heat and release.Therefore, infrared ray is commonly referred to as heat ray.It is logical It crosses using above-mentioned insulation particle, can effectively shield infrared ray (heat ray).It should be noted that so-called insulation particle, it is intended that The particle of infrared ray can be absorbed.
It as the concrete example of above-mentioned insulation particle, can enumerate: the tin oxide grain of the tin oxide particles of adulterated al, doped indium The zinc oxide particles of son, the tin oxide particles (ATO particle) of antimony dopant, the zinc oxide particles (GZO particle) of doped gallium, doped indium The zinc oxide particles (AZO particle) of (IZO particle), adulterated al, the Titanium particles for adulterating niobium, sodium contaminated tungsten oxide particle, The tungsten oxide particle for adulterating caesium, the tungsten oxide particle for adulterating thallium, the indium oxide particle for adulterating the tungsten oxide particle of rubidium, doped tin Metal oxide particles or the lanthanum hexaboride such as zinc oxide particles of (ITO particle), the zinc oxide particles of doped tin, doped silicon (LaB6) particle etc..The insulation particle other than these can also be used.It is preferably golden since the function of shielding of heat ray is higher Belong to oxide particle, more preferably ATO particle, GZO particle, IZO particle, ITO particle or tungsten oxide particle, especially preferably ITO particle or tungsten oxide particle.Be particularly due to heat ray function of shielding it is higher and be easy obtain, therefore preferably adulterate The indium oxide particle (ITO particle) of tin, preferably also tungsten oxide particle.
From the viewpoint of further increasing the thermal insulation of intermediate coat and laminated glass, tungsten oxide particle preferably adulterates gold The tungsten oxide particle of category.Above-mentioned " tungsten oxide particle " includes the tungsten oxide particle of doping metals.Oxygen as above-mentioned doping metals Change tungsten particle, it is specific enumerable: the tungsten oxide particle of sodium contaminated, the tungsten oxide particle for adulterating caesium, the tungsten oxide particle for adulterating thallium And the tungsten oxide particle etc. of doping rubidium.
From the viewpoint of further increasing the thermal insulation of intermediate coat and laminated glass, the oxidation of caesium is especially preferably adulterated Tungsten particle.From the viewpoint of further increasing the thermal insulation of intermediate coat and laminated glass, the tungsten oxide particle of the doping caesium is excellent It is selected as formula: Cs0.33WO3Represented tungsten oxide particle.
The average grain diameter of above-mentioned insulation particle is preferably 0.01 μm or more, and more preferably 0.02 μm or more, additionally, it is preferred that being 0.1 μm hereinafter, more preferably 0.05 μm or less.If average grain diameter is above-mentioned lower limit or more, the shielding of heat ray sufficiently becomes It is high.If average grain diameter be the above-mentioned upper limit hereinafter, if the dispersibility of insulation particle get higher.
Above-mentioned " average grain diameter " indicates volume average particle size.Particle size distribution device (day machine dress can be used in average grain diameter Company manufacture " UPA-EX150 ") etc. be measured.
In position (first layer, the second layer, third layer or side covering portion) 100 weight % comprising above-mentioned insulation particle In, the content of above-mentioned insulation particle is preferably 0.01 weight % or more, more preferably 0.1 weight % or more, and further preferably 1 Weight % or more, especially preferably 1.5 weight % or more.In position (first layer, the second layer, comprising above-mentioned insulation particle Three layers or side covering portion) in 100 weight %, the content of above-mentioned insulation particle is preferably 6 weight % hereinafter, more preferably 5.5 Weight % hereinafter, further preferably 4 weight % hereinafter, especially preferably 3.5 weight % hereinafter, most preferably 3 weight % with Under.If above-mentioned insulation particle content be above-mentioned lower limit or more and the above-mentioned upper limit hereinafter, if thermal insulation sufficiently get higher, and visible light Transmissivity is sufficiently got higher.
(metal salt)
Above-mentioned intermediate coat also may include at least one kind of metal salt in alkali metal salt, alkali salt and Mg salt (below sometimes It is recorded as metal salt M).Above-mentioned first layer may include above-mentioned metal salt M.The above-mentioned second layer may include above-mentioned metal salt M.Above-mentioned Three layers may include above-mentioned metal salt M.Above-mentioned side covering portion may include above-mentioned metal salt M.Above-mentioned superficial layer preferably comprises above-mentioned Metal salt M.By using above-mentioned metal salt M, in the cementability or intermediate coat of easily controllable intermediate coat and laminated glass member The cementability of each interlayer.Above-mentioned metal salt M can be used only a kind, also can be used in combination two or more.
Above-mentioned metal salt M preferably comprises at least one kind of metal in Li, Na, K, Rb, Cs, Mg, Ca, Sr and Ba.In Between metal salt contained in film preferably comprise at least one kind of metal in K and Mg.
In addition, above-mentioned metal salt M is more preferably the alkali metal salt of the organic acid of carbon atom number 2~16, carbon atom number 2~16 Organic acid alkali salt or carbon atom number 2~16 organic acid Mg salt, further preferably carbon atom number 2~16 The carboxylic acid potassium salt of carboxylic acid magnesium salts or carbon atom number 2~16.
As the carboxylic acid magnesium salts of above-mentioned carbon atom number 2~16 and the carboxylic acid potassium salt of above-mentioned carbon atom number 2~16, can arrange It lifts: magnesium acetate, potassium acetate, propionic acid magnesium, potassium propionate, 2 Ethylbutanoic acid magnesium, 2 Ethylbutanoic acid potassium, 2 ethyl hexanoic acid magnesium and 2- second Base caproic acid potassium etc..
Mg's and K in position (first layer, the second layer, third layer or side covering portion) comprising above-mentioned metal salt M contains The summation of amount is preferably 5ppm or more, more preferably 10ppm or more, further preferably 20ppm or more, additionally, it is preferred that being 300ppm hereinafter, more preferably 250ppm hereinafter, further preferably 200ppm or less.If the summation of the content of Mg and K is upper Lower limit or more is stated and the above-mentioned upper limit hereinafter, can then control the cementability or intermediate coat of intermediate coat and laminated glass member better In each interlayer cementability.
(ultraviolet light screener)
Above-mentioned intermediate coat also may include ultraviolet light screener.Above-mentioned first layer may include ultraviolet light screener.Above-mentioned Two layers may include ultraviolet light screener.Above-mentioned third layer may include ultraviolet light screener.Above-mentioned side covering portion may include ultraviolet Line screener.By using ultraviolet light screener, even if intermediate coat and laminated glass are by being used for a long time, it is seen that light transmission Also more it is not easy to reduce.Above-mentioned ultraviolet light screener can be used only a kind, also can be used in combination two or more.
Above-mentioned ultraviolet light screener includes ultraviolet absorbing agent.Above-mentioned ultraviolet light screener is preferably ultraviolet absorbing agent.
As above-mentioned ultraviolet light screener, such as can enumerate: the ultraviolet light screener comprising metallic atom includes metal oxygen The ultraviolet light screener of compound, the ultraviolet light screener with benzotriazole structure, the ultraviolet screen with benzophenone structural It covers agent, the ultraviolet light screener with triazine structure, the ultraviolet light screener with malonate structure, there is oxanilide knot The ultraviolet light screener of structure and the ultraviolet light screener with benzoate structure etc..
As the above-mentioned ultraviolet light screener comprising metallic atom, such as can enumerate: platinum particles utilize coated with silica Particle made of particle made of platinum particles surface, palladium particle and utilization coated with silica palladium particle surface etc..Ultraviolet light Screener is preferably not insulation particle.
Above-mentioned ultraviolet light screener is preferably the ultraviolet light screener with benzotriazole structure, has benzophenone structural Ultraviolet light screener, the ultraviolet light screener with triazine structure or the ultraviolet light screener with benzoate structure.On Stating ultraviolet light screener more preferably has the ultraviolet light screener of benzotriazole structure or with the ultraviolet of benzophenone structural Line screener, further preferably with the ultraviolet light screener of benzotriazole structure.
It as the above-mentioned ultraviolet light screener comprising metal oxide, such as can enumerate: zinc oxide, titanium oxide and oxidation Cerium etc..In turn, about the above-mentioned ultraviolet light screener comprising metal oxide, surface can also have passed through cladding.As above-mentioned The covering material on the surface of the ultraviolet light screener comprising metal oxide can be enumerated: insulating properties metal oxide water-disintegrable has Organic silicon compound and silicone compounds etc..
It as the above-mentioned ultraviolet light screener with benzotriazole structure, such as can enumerate: 2- (2'- hydroxyl -5'- methyl Phenyl) benzotriazole (" the Tinuvin P " of BASF AG's manufacture), 2- (2'- hydroxyl -3', 5'- di-tert-butyl-phenyl) benzo three Azoles (" Tinuvin 320 " of BASF AG's manufacture), 2- (2'- hydroxyl -3'- tert-butyl -5- aminomethyl phenyl) -5- chlorobenzotriazole (BASF is public for (" Tinuvin 326 " of BASF AG's manufacture) and 2- (2'- hydroxyl -3', 5'- diamyl phenyl) benzotriazole Take charge of " Tinuvin 328 " of manufacture) etc..Due to absorbing haveing excellent performance for ultraviolet light, above-mentioned ultraviolet light screener is preferably The ultraviolet light screener with benzotriazole structure comprising halogen atom more preferably has benzotriazole knot comprising chlorine atom The ultraviolet light screener of structure.
As the above-mentioned ultraviolet light screener with benzophenone structural, such as octabenzone (BASF AG's system can be enumerated " Chimassorb 81 " made) etc..
As the above-mentioned ultraviolet light screener with triazine structure, such as " LA-F70 " of ADEKA company manufacture can be enumerated And 2- (4,6- diphenyl -1,3,5- triazine -2- base) -5- [(hexyl) oxygroup]-phenol (" Tinuvin of BASF AG's manufacture 1577FF ") etc..
It as the above-mentioned ultraviolet light screener with malonate structure, can enumerate: 2- (to methoxybenzylidene) third Acid dimethyl, 2,2- (1,4- phenylenedimethylidyne) dimalonic acid tetra-ethyl ester, 2- (to methoxybenzylidene)-bis- (1,2,2, 6,6- pentamethyl 4- piperidyl) malonate etc..
As the commercially available product of the above-mentioned ultraviolet light screener with malonate structure, can enumerate: Hostavin B-CAP, Hostavin pR-25, Hostavin pR-31 (being manufactured by Clariant company).
It as the above-mentioned ultraviolet light screener with oxanilide structure, can enumerate: N- (2- ethylphenyl)-N'- (2- second Oxygroup -5- tert-butyl-phenyl) Oxalic acid diamides, N- (2- ethylphenyl)-N'- (2- ethoxyl phenenyl) Oxalic acid diamides, 2- second Have on the nitrogen-atoms such as base -2'- ethyoxyl-oxanilide (" the Sanduvor VSU " of the manufacture of Clariant company) substituted The Oxalic acid diamides class of aryl etc..
As the above-mentioned ultraviolet light screener with benzoate structure, such as 3,5- di-t-butyl -4- hydroxyl can be enumerated Benzoic acid 2,4- 6- di-tert-butyl phenyl ester (" Tinuvin 120 " of BASF AG's manufacture) etc..
In position (first layer, the second layer, third layer or side covering portion) 100 weights comprising above-mentioned ultraviolet light screener It measures in %, the content of above-mentioned ultraviolet light screener is preferably 0.1 weight % or more, more preferably 0.2 weight % or more, further Preferably 0.3 weight % or more, especially preferably 0.5 weight % or more.At the position (first comprising above-mentioned ultraviolet light screener Layer, the second layer, third layer or side covering portion) in 100 weight %, the content of above-mentioned ultraviolet light screener is preferably 2.5 weights Measure % hereinafter, more preferably 2 weight % hereinafter, further preferably 1 weight % hereinafter, especially preferably 0.8 weight % or less. If above-mentioned ultraviolet light screener content be above-mentioned lower limit more than and the above-mentioned upper limit hereinafter, if can further suppress by one section when Between after transmission of visible light reduction.It is upper in the 100 weight % of layer comprising above-mentioned ultraviolet light screener especially by making The content for stating ultraviolet light screener is 0.2 weight % or more, can significantly inhibit intermediate coat and laminated glass when by one section Between after transmission of visible light reduction.
(antioxidant)
Above-mentioned intermediate coat also may include antioxidant.Above-mentioned first layer may include antioxidant.The above-mentioned second layer may include Antioxidant.Above-mentioned third layer may include antioxidant.Above-mentioned side covering portion may include antioxidant.Above-mentioned antioxidant can Using only a kind, two or more also can be used in combination.
It as above-mentioned antioxidant, can enumerate: phenol antioxidant, sulphur class antioxidant and phosphorus antioxidants etc.. Above-mentioned phenol antioxidant is the antioxidant with phenol skeleton.Above-mentioned sulphur class antioxidant is to contain the anti-oxidant of sulphur atom Agent.Above-mentioned phosphorus antioxidants are the antioxidant containing phosphorus atoms.
Above-mentioned antioxidant is preferably phenol antioxidant or phosphorus antioxidants.
It as above-mentioned phenol antioxidant, can enumerate: 2,6-di-tert-butyl p-cresol (BHT), butylated hydroxyanisole (BHA) (BHA), 2,6- di-t-butyl -4- ethyl -phenol, β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid stearyl ester, 2,2'- methylene Base bis- (4- methyl -6- butylphenols), 2,2' methylene bis (4- ethyl -6- tert-butyl phenol), 4,4'- fourth pitch bis- (3- first Base -6- tert-butyl phenol), 1,1,3- tri- (2- methylhydroxy -5- tert-butyl-phenyl) butane, four [methylene -3- (3', 5'- fourths Base -4- hydroxy phenyl) propionic ester] methane, 1,3,3- tri- (2- methyl -4- hydroxyl -5- tert-butyl phenol) butane, 1,3,5- front three Base -2,4,6- three (3,5- di-tert-butyl-4-hydroxyl benzyl) benzene, bis- (3,3'- tert-butyl phenol) butyric acid diol esters and bis- (3- Tertiary butyl-4-hydroxy -5- methyl benzenpropanoic acid) ethylenebis (oxygroup ethylidene) ester etc..It can be suitably used in these antioxidants It is one kind or two or more.
It as above-mentioned phosphorus antioxidants, can enumerate: tridecyl phosphite, phosphorous acid three (tridecyl) ester, phosphorous acid Triphenylmethyl methacrylate, trisnonyl phenyl phosphite, bis- (tridecyl) pentaerythritol diphosphites, bis- two phosphorous of (decyl) pentaerythrite Bis- (2,4- di-t-butyl -6- aminomethyl phenyl) ethyl esters of acid esters, phosphorous acid three (2,4- di-tert-butyl-phenyl) ester, phosphorous acid and 2,2' methylene bis (4,6- di-t-butyl -1- phenoxy group) (2- ethyl hexyl oxy) phosphorus etc..These antioxidants can be suitably used In it is one kind or two or more.
It as the commercially available product of above-mentioned antioxidant, such as can enumerate: " IRGANOX 245 ", the BASF of BASF AG's manufacture " IRGAFOS 168 " of company's manufacture, " IRGAFOS 38 " of BASF AG's manufacture, Sumitomo Chemical Co. Ltd. manufacture " IRGANOX 1010 " etc. of " Sumilizer BHT " and BASF AG manufacture.
In order to make intermediate coat and laminated glass keep higher transmission of visible light for a long time, in above-mentioned 100 weight of intermediate coat It measures in % or in position (first layer, the second layer, third layer or side covering portion) 100 weight % comprising antioxidant, it is above-mentioned The content of antioxidant is preferably 0.1 weight % or more.In addition, the additive effect due to antioxidant can reach saturation, In above-mentioned 100 weight % of intermediate coat or in the 100 weight % of layer comprising above-mentioned antioxidant, the content of above-mentioned antioxidant is excellent It is selected as 2 weight % or less.
(other compositions)
Above-mentioned first layer, the above-mentioned second layer, above-mentioned third layer and above-mentioned side covering portion can according to need respectively and Contain: coupling agent, dispersing agent, surfactant, fire retardant, antistatic agent, pigment, dyestuff, moisture-proof comprising silicon, aluminium or titanium The additives such as agent, crosslinking agent, fluorescent bleaches and infrared absorbent.These additives can be used only a kind, and can also combine makes Use two or more.
(other detailed descriptions of intermediate film for laminated glasses)
One end of above-mentioned intermediate coat is preferably 0.5m or more at a distance from the other end, more preferably 0.8m or more, especially excellent It is selected as 1m or more, additionally, it is preferred that being 3m hereinafter, more preferably 2m is hereinafter, especially preferably 1.5m or less.There is length in intermediate coat In the case where spending direction and width direction, one end is the distance of the length direction of intermediate coat at a distance from the other end.In centre In the case that film has the flat shape of square, one end be at a distance from the other end it is opposite to one end and the other end away from From.
The thickness of above-mentioned intermediate coat is not particularly limited.From the viewpoint in practical face and sufficiently improve the resistance to of laminated glass From the perspective of penetrability and flexual rigidity, the thickness of intermediate coat is preferably 0.1mm or more, more preferably 0.25mm or more, separately Outside, preferably 3mm hereinafter, more preferably 2mm hereinafter, further preferably 1.5mm or less.If intermediate coat with a thickness of under above-mentioned More than limit, then the penetration resistance of laminated glass and flexual rigidity are got higher.If intermediate coat with a thickness of the above-mentioned upper limit hereinafter, if in Between the hyalinosis of film obtain more preferably.
The thickness of intermediate coat is denoted as T.The thickness of above-mentioned first layer is preferably 0.06T or more, more preferably 0.0625T with On, further preferably 0.1T or more, additionally, it is preferred that being 0.4T hereinafter, more preferably 0.375T is hereinafter, further preferably 0.25T is hereinafter, further preferably 0.15T or less.If above-mentioned first layer with a thickness of 0.4T hereinafter, if flexual rigidity become more It is good.In addition, if above-mentioned first layer with a thickness of above-mentioned lower limit more than, sound-proofing further increases.
The above-mentioned second layer and each thickness of above-mentioned third layer are preferably 0.3T or more, more preferably 0.3125T or more, into One step is preferably 0.375T or more, additionally, it is preferred that being 0.9375T hereinafter, more preferably 0.9T or less.The above-mentioned second layer and on Each thickness for stating third layer is also possible to 0.46875T hereinafter, being also possible to 0.45T or less.In addition, if the above-mentioned second layer and Above-mentioned third layer it is each with a thickness of more than above-mentioned lower limit and the above-mentioned upper limit is hereinafter, then the rigidity of laminated glass and sound-proofing are further It improves.
The above-mentioned second layer and the aggregate thickness of above-mentioned third layer are preferably 0.625T or more, more preferably 0.75T or more, into One step is preferably 0.85T or more, additionally, it is preferred that being 0.9375T hereinafter, more preferably 0.9T or less.In addition, if the above-mentioned second layer With the aggregate thickness of above-mentioned third layer be above-mentioned lower limit or more and the above-mentioned upper limit hereinafter, then the rigidity of laminated glass and sound-proofing into One step improves.
Above-mentioned intermediate coat can be intermediate coat in homogeneous thickness, be also possible to the intermediate coat of thickness change.Above-mentioned intermediate coat Section shape can be rectangle, be also possible to wedge shape.
The manufacturing method of intermediate coat of the invention is not particularly limited.As the manufacturing method of intermediate coat of the invention, example Can such as method be listed below:, will be obtained each after being respectively formed each layer to each resin combination for forming each layer The method of layer laminate；And it will be coextruded to each resin combination for forming each layer using extruder, thus laminating layers Method.Due to being adapted for continuous production, the manufacturing method of extrusion molding is preferably carried out.
From the manufacture efficiency of intermediate coat it is excellent from the aspect of, the preferably above-mentioned second layer and above-mentioned third layer include same Kind polyvinyl acetal resin.From the manufacture efficiency of intermediate coat it is excellent from the aspect of, the more preferable above-mentioned second layer and above-mentioned the Three layers include same polyvinyl acetal resin and same plasticizer.From the manufacture efficiency of intermediate coat it is excellent in terms of Consider, the further preferred above-mentioned second layer is formed with above-mentioned third layer by same resin combination.
At least one surface of above-mentioned intermediate coat preferably in the surface of two sides has concaveconvex shape.Above-mentioned intermediate coat is more excellent The surface for being selected in two sides has concaveconvex shape.As the method for forming above-mentioned concaveconvex shape, it is not particularly limited, such as can arrange Lift: die lip is embossed (rip emboss) method, dandy roll method, calendering rod method and section bar extrusion method etc..Due to can quantitatively be formed The embossing of multiple concaveconvex shapes of constant relief pattern, therefore preferably dandy roll method.
(laminated glass)
Figure 12 is the cross-sectional view for schematically showing the laminated glass of the 1st embodiment.
Laminated glass 31 shown in Figure 12 has the 1st laminated glass member 21, the 2nd laminated glass member 22 and centre Film 11.In laminated glass 31, intermediate coat 11 shown in FIG. 1 has been used.Intermediate coat 11 is arranged and is sandwiched in the 1st laminated glass portion Between part 21 and the 2nd laminated glass member 22.
There is the 1st laminated glass member 21 in the 1st surface (the 1st interarea) lamination of intermediate coat 11.In intermediate coat 11 and the 1st Opposite the 2nd surface (the 2nd interarea) lamination in surface has the 2nd laminated glass member 22.Surface stack in the outside of first layer 1 has 1st laminated glass member 21.Surface stack in the outside of third layer 3 has the 2nd laminated glass member 22.
In laminated glass 31, the outer surface of side covering portion 4 and laminated glass component parts 21 and laminated glass are constituted The side of component 22 is connected.In laminated glass 31, first layer 1 is coated by side covering portion 4, therefore first layer 1 does not expose.
Figure 13 is the cross-sectional view for schematically showing the laminated glass of the 2nd embodiment.
Laminated glass 31X shown in Figure 13 has the 1st laminated glass member 21X, the 2nd laminated glass member 22X, Yi Jizhong Between film 11X.Intermediate coat 11X has first layer 1X and metallic cover portion 4X.
There is the 1st laminated glass member 21X in the 1st surface (the 1st interarea) lamination of intermediate coat 11X.Intermediate coat 11 with Opposite the 2nd surface (the 2nd interarea) lamination in 1st surface has the 2nd laminated glass member 22X.
In laminated glass 31X, side covering portion 4X extends to laminated glass component parts 21X and laminated glass is constituted On the side of component 22X.In laminated glass 31X, first layer 1X is coated by side covering portion 4X, therefore first layer 1 does not reveal Out.In laminated glass 31X, the side of laminated glass component parts 21X and laminated glass component parts 22X are coated by side Portion 4X is coated, therefore the side of laminated glass component parts 21X and laminated glass component parts 22X are not exposed.
Can also be as laminated glass 31, the side covering portion of intermediate coat extends to the 1st laminated glass member and the 2nd In at least part of the side of laminated glass member.The side covering portion of intermediate coat can also not extend to the 1st laminated glass The side of component and the 2nd laminated glass member.
It as above-mentioned laminated glass member, can enumerate: glass plate and PET (polyethylene terephthalate) film etc.. Laminated glass other than including to sandwich the laminated glass of intermediate coat between two glass sheets, further include glass plate with The laminated glass of intermediate coat is sandwiched between PET film etc..Above-mentioned laminated glass is the laminated body for having glass plate, is preferably at least made With a glass sheets.It is preferred that above-mentioned 1st laminated glass member and above-mentioned 2nd laminated glass member are respectively glass plate or PET Film, and above-mentioned laminated glass has glass plate as in above-mentioned 1st laminated glass member and above-mentioned 2nd laminated glass member At least one.It is preferred that both above-mentioned 1st laminated glass member and above-mentioned 2nd laminated glass member are glass plate (the 1st glass Plate and the 2nd glass plate).Above-mentioned intermediate coat is suitable for being arranged between the 1st glass plate and the 2nd glass plate and to obtain interlayer Glass.
It as above-mentioned glass plate, can enumerate: unorganic glass and organic glass.It as above-mentioned unorganic glass, can enumerate: floating Method plate glass, heat ray absorb glass sheet, heat ray reflection glass sheet, polishing plate glass, pattern glass and wired flat Glass sheet etc..Above-mentioned organic glass is the synthetic resin glass instead of unorganic glass.It as above-mentioned organic glass, can enumerate: poly- Carbonic ester plate and poly- (methyl) acrylic acid resin plate etc..As above-mentioned poly- (methyl) acrylic acid resin plate, can enumerate poly- (methyl) methyl acrylate plate etc..
The thickness of above-mentioned laminated glass member is preferably 1mm or more, additionally, it is preferred that be 5mm hereinafter, more preferably 3mm with Under.In addition, the thickness of the glass plate is preferably 0.5mm or more, more excellent in the case where above-mentioned laminated glass member is glass plate It is selected as 0.7mm or more, additionally, it is preferred that being 5mm hereinafter, more preferably 3mm or less.It is PET film in above-mentioned laminated glass member In the case of, the thickness of the PET film is preferably 0.03mm or more, additionally, it is preferred that being 0.5mm or less.
The manufacturing method of above-mentioned laminated glass is not particularly limited.Firstly, in above-mentioned 1st laminated glass member and above-mentioned the It sandwiches intermediate coat between 2 laminated glass members and obtains laminated body.Then, such as by making obtained laminated body pass through extruding Roller carries out decompression pumping by being loaded into rubber bag, thus by above-mentioned 1st laminated glass member, above-mentioned 2nd interlayer glass Remaining air is de-gassed between glass component and intermediate coat.Thereafter, at about 70~110 DEG C carry out pre-glued and obtain by The laminated body of pre-pressing.Then, the laminated body that have passed through pre-pressing is put into autoclave or is pressurizeed to it, about It is pressed under 120~150 DEG C and 1~1.5mPa of pressure.Laminated glass so can be obtained.Manufacturing above-mentioned laminated glass When, first layer, the second layer and third layer can also be subjected to lamination.
Above-mentioned intermediate coat and above-mentioned laminated glass can be used for automobile, rail vehicle, aircraft, ship and building etc.. Above-mentioned intermediate coat and above-mentioned laminated glass can also be used for the purposes other than these.Above-mentioned intermediate coat and above-mentioned laminated glass are excellent It is selected as vehicle use or intermediate coat and laminated glass for building, more preferably for motor vehicle intermediate coat and laminated glass.On It states intermediate coat and above-mentioned laminated glass can be used for windshield, side window glass, rear window or skylight glass of automobile etc..On It states intermediate coat and above-mentioned laminated glass is suitable for automobile.Above-mentioned intermediate coat can be used for obtaining the laminated glass of automobile.
Hereinafter, disclosing embodiment and the present invention being described in more detail.The present invention is not limited to these embodiments.
Prepare material below.
(resin)
Polyvinyl acetal resin:
Polyvinyl acetal resin shown in following table 1 is used.Used whole polyvinyl acetal resin is in contracting The n-butanal of carbon atom number 4 is used when hydroformylation.About polyvinyl acetal resin, acetalizing degree (butyralization degree), acetyl Change degree and hydroxyl containing ratio are measured by the method according to JIS K6728 " polyvinyl butyral test method ".It needs It is noted that also showing and in the case where being measured by ASTM D1396-92 according to JIS K6728 " poly- second The identical numerical value of method of enol butyral test method ".
Polyester resin:
PEs1 (manufacture of UE3220, Unitika company)
PEs2 (manufacture of UE3223, Unitika company)
(methyl) acrylic polymer:
Pass through obtained (methyl) acrylic polymer Ac1, Ac2, Ac3 and the Ac4 of synthetic method below
It sandwiches between PET sheet (Nippa company manufacture, thickness 50 μm) of the two panels through single side demoulding processing with following tables The polymerizable composition, polymerizable composition that composition is mixed shown in 3 forms 100 μm of thickness of polymerizable composition, polymerizable composition layer.Wherein, in two panels PET Spacer is provided with around piece.Using high-pressure mercury UV lamp, with exposure 3000mJ/cm2Polymerizable composition, polymerizable composition layer is irradiated Thus ultraviolet light makes polymerizable composition, polymerizable composition reacted and solidifies, obtained (methyl) acrylic polymer Ac1, Ac2, Ac3, Ac4 and Ac5.
Polyvinyl acetate:
Pass through the obtained polyvinyl acetate PVAc1 of synthetic method below
The glass system aggregation container equipped with reflux condenser, dropping funel, thermometer and nitrogen inlet is prepared. 100 parts by weight of vinyl acetate monomer, 1.0 parts by weight of 3- methyl -3- butyl -1- alcohol, Yi Jijia are added into the aggregation container 3.8 parts by weight of alcohol are heated and are stirred and to progress nitrogen displacement in aggregation container.Then, make in above-mentioned aggregation container Temperature reach 60 DEG C, last 4 hours be added dropwise as 0.02 parts by weight of new peroxide tert-butyl caprate of polymerization initiator, acetic acid 1.5 parts by weight of 150 parts by weight of vinyl acetate monomer and 3- methyl -3- butyl -1- alcohol, carry out polymerizeing for 2 hours after completion of dropwise addition, The solution comprising polyvinyl acetate is obtained.The solution is 3 hours dry in 110 DEG C of baking oven, result in poly- second Vinyl acetate PVAc1.
(plasticizer)
Triethylene glycol two (2 ethyl hexanoic acid ester) (3GO)
Benzoic acids plasticizer (manufacture of PB-3A, DIC company) (P1)
Adipic acid two (2- butoxyethyl group) ester (DBEA)
Bis- (2- butoxyethyl group) esters (D931) of adipic acid
(compound (A))
Compound (A1) (KE-311, Arakawa Chemical Industries company manufacture, 95 DEG C of softening point)
Compound (A2) (manufacture of Enpara 70, Ajinomoto Fine-Techno company, 100 DEG C of softening point)
(ultraviolet light screener)
Tinuvin 326 (2- (2'- hydroxyl -3'- tert-butyl -5- aminomethyl phenyl) -5- chlorobenzotriazole, BASF AG's system " Tinuvin 326 " made)
(antioxidant)
BHT (DBPC 2,6 ditertiary butyl p cresol)
(metal salt)
Mg mixture (50:50 (weight ratio) mixture of 2 Ethylbutanoic acid magnesium and magnesium acetate)
(embodiment 1)
It is used to form the preparation of the composition of first layer:
By 100 parts by weight of polyvinyl acetal resin of type shown in following table 1,75 parts by weight of plasticizer (3GO), change Close object (A1) (KE-311) 100 parts by weight, 0.2 parts by weight of ultraviolet light screener (Tinuvin 326) and antioxidant (BHT) 0.2 parts by weight are mixed, and have obtained the composition for being used to form first layer.
It is used to form the preparation of the composition of the second layer and third layer (comprising side covering portion):
By 100 parts by weight of polyvinyl acetal resin of type shown in following table 1,35 parts by weight of plasticizer (3GO), purple 0.2 parts by weight of outside line screener (Tinuvin 326), 0.2 parts by weight of antioxidant (BHT) and make obtained intermediate coat The Mg mixture for the amount that middle metallic element concentration (Mg concentration) reaches 70ppm is mixed, obtained being used to form the second layer and The composition of third layer.
The production of intermediate coat:
Using coextruder, by the composition for being used to form first layer and the composition for being used to form the second layer and third layer Coextrusion, is thus prepared for having the second layer (340 μm of thickness)/first layer (100 μm of thickness)/third layer (340 μm of thickness) The intermediate coat (780 μm of thickness) of laminated construction.
In extrusion molding, the second layer is set to extend to the center of the side of first layer, and third layer is made to extend to first layer Side center, to constitute side covering portion by the second layer and third layer.In obtained intermediate coat, first layer Entire side coated by side covering portion.
The preparation (sound-proofing measurement is used) of laminated glass A:
The central portion of obtained intermediate coat is cut into long 6.5cm × wide 6.5cm size.Then, according to JIS Intermediate coat is sandwiched between the two panels green glass (long 6.5cm × wide 6.5cm × thickness 2mm) of R3208, obtains laminated body.It should Laminated body is packed into rubber bag, after twenty minutes with the vacuum degree degassing of 2.6KPa, keeps degassing phase to move into baking oven, Jin Er It is kept for 30 minutes at 90 DEG C, carries out vacuum pressed, pre-pressing has been carried out to laminated body.In autoclave, in 135 DEG C and pressure Under conditions of 1.2mPa, the laminated body that have passed through pre-pressing press within 20 minutes, laminated glass A has been obtained.
The preparation (foaming of end, which is evaluated, to be used) of laminated glass B:
Obtained intermediate coat is cut into long 10cm × wide 10cm size.For the intermediate coat with side covering portion Situation, by make the end at least 1 side there are side covering portion in a manner of cut intermediate coat.Then, washing and drying have passed through Two panels transparent float glass (long 10cm × wide 10cm × thickness 2.5mm) between sandwich intermediate coat, obtain laminated body.This is folded Layer body is packed into rubber bag, after twenty minutes with the vacuum degree degassing of 2.6KPa, keeps degassing phase to move into baking oven, and then 90 It is kept for 30 minutes at DEG C, carries out vacuum pressed, pre-pressing has been carried out to laminated body.In autoclave, in 135 DEG C and pressure Under conditions of 1.2MPa, the laminated body that have passed through pre-pressing press within 20 minutes, laminated glass B has been obtained.
The preparation (plate offset evaluation is used) of laminated glass C:
Obtained intermediate coat is cut into long 30cm × wide 15cm size.For the intermediate coat with side covering portion Situation, by make the end of horizontal edge there are side covering portion in a manner of cut intermediate coat.Then, it have passed through washing and drying two Intermediate coat is sandwiched between piece transparent float glass (long 30cm × wide 15cm × thickness 3.0mm), obtains laminated body.By the laminated body It is packed into rubber bag, after twenty minutes with the vacuum degree degassing of 2.6KPa, keeps degassing phase to move into baking oven, and then at 90 DEG C It is kept for 30 minutes, carries out vacuum pressed, pre-pressing has been carried out to laminated body.In autoclave, at 135 DEG C and pressure 1.2MPa Under conditions of, the laminated body that have passed through pre-pressing press within 20 minutes, laminated glass C has been obtained.
(embodiment 2~12)
The composition for being used to form first layer is set as shown in following table 1,2 and is used to form the second layer and third layer Composition used in thermoplastic resin and plasticizer type and combined amount, in addition to this, similarly to Example 1 Intermediate coat and laminated glass are arrived.In addition, in embodiment 2~12 and following Comparative Examples 1 and 2, with same as Example 1 Use level (being 0.2 parts by weight relative to 100 parts by weight of polyvinyl acetal resin) has cooperated the purple of type same as Example 1 Outside line screener and antioxidant (make metallic element concentration in intermediate coat (Mg concentration) with use level same as Example 1 Reach the amount of 70ppm) cooperate the Mg mixture of type same as Example 1.
It should be noted that in embodiment 7, relative to 100 parts by weight of thermoplastic resin, respectively with the use of 60 parts by weight Compound (A1) and compound (A2).
(comparative example 1)
Not using the side of second, third layer of cladding first layer, in addition to this, obtain similarly to Example 1 intermediate Film and laminated glass.
(comparative example 2)
Not using the side of second, third layer of cladding first layer, in addition to this, obtain similarly to Example 3 intermediate Film and laminated glass.
(embodiment 13)
The production of first layer:
(methyl) acrylic polymer Ac1 obtained above (layer comprising solidfied material, 100 μm of thickness) is prepared.
The production of the second layer and third layer:
It is used to form the preparation of the composition of second, third layer:
Gradation composition below is mixed, is sufficiently kneaded using mixing mill, has obtained the group for being used to form second, third layer Close object.
100 parts by weight of polyvinyl acetal resin (PVB)
35 parts by weight of plasticizer (3GO)
The Mg in second, third obtained layer is set to reach the metal salt M (Mg mixture) of the amount of 70ppm
Reach the ultraviolet light screener (Tinuvin 326) of the amount of 0.2 weight % in second, third obtained layer
Reach the antioxidant (BHT) of the amount of 0.2 weight % in second, third obtained layer
The obtained composition for being used to form second, third layer is squeezed out using extruder, has obtained second, third layer (thickness is respectively 380 μm).
The production of intermediate coat:
In the outside lamination second layer and third layer of first layer.Using roller laminator, (ACCO Brands Japan is public Take charge of " GDRB316A3 " of manufacture), it is laminated, is resulted in the second layer/the first under 100 DEG C and speed setting 3 The intermediate coat of the structure of layer/third layer.
In lamination, the second layer is made to extend to the center of the side of first layer, and third layer is made to extend to the side of first layer The center in face, to constitute side covering portion by the second layer and third layer.In obtained intermediate coat, first layer it is entire Side is coated by side covering portion.
The production of laminated glass:
Using obtained intermediate coat, in addition to this, laminated glass has been obtained similarly to Example 1.
(embodiment 14~16)
The type and use level of gradation composition are set as described in Table 4, in addition to this, similarly to Example 13 Ground has obtained intermediate coat and laminated glass.In addition, in embodiment 14~16, with use level identical with embodiment 13 ( Use level in second, third layer) cooperated ultraviolet light screener and antioxidant with 13 identical type of embodiment, with The identical use level of embodiment 13 (use level in second, third layer) has cooperated to be mixed with the Mg of 13 identical type of embodiment Object.
(embodiment 17)
It is used to form the preparation of the composition of first layer:
Gradation composition below is mixed, is sufficiently kneaded using mixing mill, has obtained the composition for being used to form first layer.
100 parts by weight of polyvinyl acetate PVAc1
70 parts by weight of plasticizer (D931)
Reach the ultraviolet light screener (Tinuvin 326) of the amount of 0.2 weight % in obtained first layer
Reach the antioxidant (BHT) of the amount of 0.2 weight % in obtained first layer
It is used to form the preparation of the composition of second, third layer:
Gradation composition below is mixed, is sufficiently kneaded using mixing mill, has obtained the group for being used to form second, third layer Close object.
100 parts by weight of polyvinyl acetal resin (PVB)
30 parts by weight of plasticizer (D931)
The Mg in second, third obtained layer is set to reach the metal salt M (Mg mixture) of the amount of 70ppm
Reach the ultraviolet light screener (Tinuvin 326) of the amount of 0.2 weight % in second, third obtained layer
Reach the antioxidant (BHT) of the amount of 0.2 weight % in second, third obtained layer
The production of intermediate coat:
Using coextruder by the obtained composition for being used to form first layer and it is obtained be used to form second, the Three layers of composition squeezes out, and has obtained having the second layer (370 μm of thickness)/first layer (100 μm of thickness)/third layer (thickness 370 μm) structure intermediate coat.
In extrusion molding, the second layer is set to extend to the center of the side of first layer, and third layer is made to extend to first layer Side center, to constitute side covering portion by the second layer and third layer.In obtained intermediate coat, first layer Entire side is by side covering portion.
(evaluation)
(1) modulus of shearing
The determination of viscoelasticity of first layer has been carried out as described below.
Prepare the kneading object for being used to form the composition of first layer.Using pressure forming machine, to obtained at 150 DEG C It is kneaded object to be press-formed, has obtained the resin film of thickness 0.35mm.Obtained resin film is at 25 DEG C and relatively wet It is placed 2 hours under conditions of degree 30%.After placing 2 hours, measured using " ARES-G2 " that TA Instruments company manufactures Viscoplasticity.Use the parallel-plate of diameter 8mm as accessory.Temperature is set to be down to -50 from 30 DEG C with the cooling rate of 3 DEG C/min DEG C condition and frequency 1Hz and strain 1% under conditions of be determined.By the loss in obtained measurement result The peak temperature of angle tangent is as glass transition temperature Tg (DEG C).Wherein, by obtained intermediate coat 23 ± 2 DEG C of room temperature, It has been taken care of in the environment of relative humidity 25 ± 5% 1 month.Then, in 23 DEG C ± 2 DEG C of room temperature of environment, pass through from intermediate coat It removes and removes the second layer and third layer, result in first layer.It can also be to obtained first layer so that thickness reaches Mode to 0.35mm is press-formed at 150 DEG C and (is not added under pressure condition as 150 DEG C, 10 minutes, is under pressurized state 150 DEG C, 10 minutes) and prepare resin film.
For the second layer and third layer, also mode identical with first layer has carried out the determination of viscoelasticity of first layer.
(2) sound-proofing
Using the speaker being set in quiet room, the sound-proofing of obtained laminated glass is evaluated.Speaker For the case of the long 10cm, width 10cm, high 10cm that are composed the wood-based planet of thickness 10mm, long 7cm, width are equipped in one side The opening portion of 7cm.In addition, being provided with the music player for having loudspeaker in the inside of speaker.Then, by it is prepared to The laminated glass A of measurement sound-proofing is set to opening portion, between around clay landfill laminated glass A between opening portion Gap and laminated glass is fixed on opening portion.Preparatory typing buzzer and make at regular intervals in music player The buzzer (buzzerphone sound) of frequency 500Hz~8000Hz can be issued from loudspeaker.
Estimator listens to the sound from music player in the front for the laminated glass A for being set to speaker opening portion, and It can oneself to that whether will not become larger at specific frequency after laminated glass A passes through from the buzzerphone sound that speaker leaks out Lower frequency side equably carries out sound insulation to high frequency side and has carried out sensory evaluation.
It is evaluated as "○" the case where buzzerphone sound by no matter estimator can equably hear under what frequency, will be evaluated Person has heard under specific frequency is evaluated as "×" greater than the case where buzzerphone sound under other frequencies.
(3) foaming of end
After laminated glass B after autoclave process is placed 12 hours at 25 DEG C, 3 are toasted in 50 DEG C of baking oven It.After baking, laminated glass B is taken out from baking oven, the presence or absence of foaming within the laminated glass end 1cm that adjusts the distance carries out Evaluation.Evaluation object does not include the range around the corner of laminated glass within 1cm.Foaming according to following standard to end Determined.
[judgment criteria of the foaming of end]
Zero: having foaming
×: without foaming
(4) plate deviates
Vertical plane is fixed in the face of the side of laminated glass C, is marked in the side of laminated glass to Observed Drift amount Reference line, placed at 100 DEG C 7 days.After 7 days, the offset of two sheet glass of evaluation sample is determined and is gone forward side by side Evaluation is gone.Plate offset is determined according to following standard.
[judgment criteria of plate offset]
Zero: offset is 5mm or less
×: offset is more than 5mm
Details and result are shown in following table 1~4.It should be noted that thermoplasticity is omitted in following table 1~4 The record of gradation composition other than the resins such as resin and plasticizer.
[table 3]
The details of ingredient shown in the table 3 used when synthesizing (methyl) acrylic polymer Ac1, Ac2, Ac3 and Ac4 are such as Shown in lower.
EA: ethyl acrylate (Japanese catalyst company manufacture)
HEA: acrylic acid 2- hydroxy methacrylate (manufacture of Osaka Organic Chemical Industry company)
BzA: benzyl acrylate (manufacture of Osaka Organic Chemical Industry company, Viscoat#160)
BA: butyl acrylate (Japanese catalyst company manufacture)
AMP-20GY: phenoxy group polyethylene glycol acrylate (manufacture of chemical industrial company, the village Xin Zhong)
3GO: triethylene glycol two (2 ethyl hexanoic acid ester)
IRGACURE 184:2,2- dimethoxy -1,2- diphenylethane -1- ketone (BASF AG's manufacture)
[table 4]

Claims (19)

1. a kind of intermediate film for laminated glasses, for the intermediate film for laminated glasses with 1 layer of structure or 2 layers or more structure, Have:
First layer, with opposite the first interarea and the second interarea and connection first interarea and second master The side in face,
Side covering portion coats at least part of the side of the first layer, wherein
The first layer the coefficient of rigidity at 25 DEG C be 0.17MPa hereinafter, and the side covering portion at 25 DEG C The coefficient of rigidity be more than 1MPa.
2. intermediate film for laminated glasses according to claim 1, wherein the first layer includes thermoplastic resin, or Comprising making solidfied material made of photocurable compound or moisture-curable compound cures.
3. intermediate film for laminated glasses according to claim 1, wherein the first layer contains thermoplastic resin and plasticising Agent.
4. intermediate film for laminated glasses described in any one of claim 1 to 3, wherein the side covering portion contains Thermoplastic resin and plasticizer.
5. intermediate film for laminated glasses according to claim 1, wherein
The first layer contains thermoplastic resin and plasticizer,
The side covering portion contains thermoplastic resin and plasticizer,
Plasticizer described in the first layer compares institute relative to the content of 100 parts by weight of thermoplastic resin described in the first layer The content that plasticizer described in the covering portion of side is stated relative to 100 parts by weight of thermoplastic resin described in the side covering portion is more It is more than 15 parts by weight.
6. intermediate film for laminated glasses according to any one of claims 1 to 5, wherein the thickness of the side covering portion Degree is 0.05mm or more and 2mm or less.
7. intermediate film for laminated glasses described according to claim 1~any one of 6, wherein outside as the first layer In 1 week distance 100% of the side in week, by side covering portion cladding side distance for 15% or more and 100% or less.
8. intermediate film for laminated glasses according to any one of claims 1 to 7, wherein described in the first layer In the total surface area 100% of side, the surface area by side covering portion cladding is 15% or more and 100% or less.
9. intermediate film for laminated glasses described according to claim 1~any one of 8 is the folder with 2 layers or more structures Layer glass intermediate coat, has the second layer on first interarea for being set to the first layer.
10. intermediate film for laminated glasses according to claim 9, wherein the second layer extends to the first layer Thus at least part of the side coats at least part of the side of the first layer, thus by described second Layer constitutes the side covering portion.
11. intermediate film for laminated glasses according to claim 10, wherein the material of the second layer and the side are wrapped The material for covering portion is different.
12. the intermediate film for laminated glasses according to any one of claim 9~11, wherein the second layer contains heat Plastic resin and plasticizer.
13. the intermediate film for laminated glasses according to any one of claim 9~12, to have the above structure that haves three layers Intermediate film for laminated glasses has the third layer on second interarea for being set to the first layer.
14. intermediate film for laminated glasses according to claim 13, wherein the third layer extends to the first layer Thus at least part of the side coats at least part of the side of the first layer, thus by the third Layer constitutes the side covering portion.
15. intermediate film for laminated glasses according to claim 13, wherein the material of the third layer and the side are wrapped The material for covering portion is different.
16. intermediate film for laminated glasses described in any one of 3~15 according to claim 1, wherein the third layer contains heat Plastic resin and plasticizer.
17. intermediate film for laminated glasses described according to claim 1~any one of 16, wherein by the thickness of intermediate coat When being denoted as T, the first layer with a thickness of 0.06T or more.
18. a kind of laminated glass, has:
First laminated glass member,
Second laminated glass member and
Intermediate film for laminated glasses described in any one of claim 1~17,
It is provided among the laminated glass-use between first laminated glass member and second laminated glass member Film.
19. laminated glass according to claim 18, wherein the side covering portion of the intermediate film for laminated glasses It extends at least part of the side of first laminated glass member and second laminated glass member.
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